Ink-jet ink composition for color filter, production method for ink composition, and production meth

专利摘要:
PURPOSE: Provided are an ink-jet thermosetting ink composition used for forming a cured layer of a predetermined pattern, such as a coloring layer on a substrate of a color filter, a production method for the ink-jet thermosetting ink composition, and a method for producing a color filter using the ink-jet thermosetting ink composition. CONSTITUTION: The ink-jet ink composition for a color filter comprises: (A) an epoxy compound having two or more epoxy groups in a molecule; and (B) a carboxyl group block compound having two or more functional groups represented by the formula(1a) or formula(1b), wherein R¬1, R¬2, R¬3, R¬1', R¬2' and R¬3' each represent independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, R¬4 and R¬5 each represent independently an organic group having 1 to 18 carbon atoms, Y¬1 and Y¬1' each represent independently an oxygen atom or a sulfur atom, wherein R¬3 and R¬4 optionally are bonded with each other so as to form a heterocycle having Y¬1 as a hetero atom.
公开号:KR20020096909A
申请号:KR1020020033194
申请日:2002-06-14
公开日:2002-12-31
发明作者:니시다도모노리；니시야마마사시；사토고지；사이토순；이마세지히로
申请人:다이니폰 인사츠 가부시키가이샤；닛폰 유시 가부시키가이샤；
IPC主号:

专利说明:

Inkjet ink composition for color filters, ink composition manufacturing method, and color filter manufacturing method {INK-JET INK COMPOSITION FOR COLOR FILTER, PRODUCTION METHOD FOR INK COMPOSITION, AND PRODUCTION METHOD FOR COLOR FILTER}
[12] This invention manufactures the thermosetting ink composition for inkjets, and the thermosetting ink composition for inkjets used for forming the hardening layer of a predetermined pattern like a pixel part (coloring layer) on the board | substrate of a color filter. The method and the method of manufacturing a color filter using this thermosetting ink composition for inkjets are provided.
[13] In recent years, with the development of personal computers, in particular with the development of laptops, the demand for liquid crystal displays, especially color liquid crystal displays, tends to increase. However, since this color liquid crystal display device is expensive, the demand for cost down is increasing, and in particular, the cost down demand for a color filter having a high specific gravity in terms of cost is high.
[14] Generally, as shown in FIG. 1, the color liquid crystal display device 101 opposes the color filter 1 and the electrode substrate 2, such as a TFT substrate, and forms the clearance part 3 about 1-10 micrometers, The liquid crystal compound L is filled in this gap part 3, and the structure which enclosed the surroundings with the sealing material 4 is taken. The color filter 1 includes a black matrix layer 6 formed in a predetermined pattern to shield the boundary between pixels on the transparent substrate 5, and a plurality of colors (usually red (R), The pixel portion 7, the protective film 8, and the transparent electrode film 9, in which the three primary colors of green (G) and blue (B) light) are arranged in a predetermined order, are stacked in this order from the side closer to the transparent substrate. It takes a structure that has become. Moreover, the alignment film 10 is provided in the inner surface side of the color filter 1 and the electrode substrate 2 which opposes this. Further, in the gap portion 3, pearls 11 having a constant particle diameter are dispersed as spacers in order to maintain a constant and uniform cell gap between the color filter 1 and the electrode substrate 2. . Then, the color image is obtained by operating as a shutter by controlling the light transmittance of the liquid crystal layer behind each of the colored pixels or behind the color filter.
[15] In the case of dispersing particulate pearl 11 as shown in FIG. 1 as a spacer, the pearl is randomly dispersed regardless of the back of the black matrix layer 6 or the back of the pixel. When the pearl is disposed in the display area, i.e., the pixel portion, the part of the pearl transmits light of the backlight, and the orientation of the liquid crystal around the pearl is disturbed, thereby degrading the quality of the display image. Thus, as shown in Fig. 2, instead of dispersing the pearl, the columnar spacer having a height corresponding to the cell gap in the region of the inner surface side of the color filter and overlapping with the position where the black matrix layer 6 is formed. (12) may be formed.
[16] The details of the pixel portion of the color filter, the columnar spacer, the protective film, and the like form a coating layer of a predetermined pattern using a resin, and the coating layer is dried and solidified, and, if necessary, crosslinked again. It can form by hardening.
[17] The resin layer constituting each of these details has a common physical property such as adhesion as a film, film thickness uniformity, strength, hardness, and heat resistance that does not cause heat shrinkage or film reduction in the color filter manufacturing process. In addition to the degree of performance required, particularly high performance is required for the characteristics that are particularly important for each detail. For example, the resin layer serving as a pixel portion in which optical characteristics are important is particularly required to have excellent properties such as fineness of pattern shape, film thickness uniformity, transparency, colorability, and discoloration resistance. do. The resin layer as a black matrix layer is especially requested | required to be excellent in the fineness of a pattern shape, and light-shielding property. The resin layer as a columnar spacer which holds a cell gap is especially required to be excellent in dimensional stability even when it is excellent in strength and formed relatively thick. In addition, the resin layer as the protective film 8 covering the pixel portion is required to have sufficient hardness and adhesion to protect the pixel portion, and to have excellent transparency and excellent film thickness uniformity so as not to adversely affect the color of the pixel. Non-pollution, for example, the passivation property which can prevent the transfer of contaminants from the colored layer side to the liquid crystal so that the liquid crystal compound enclosed in the part 3 is not contaminated, and the cost that the protective film itself does not elute into the liquid crystal Outgrowth is required. The protective film 8 should have sufficient solvent resistance so as not to be dissolved or swelled when the coating liquid for forming a light distribution film is applied thereon, and washed with warm pure water or IPA (isopropanol). It is required to have sufficient resistance to water and solvent resistance to warm pure water so as not to cause film reduction or dropout.
[18] Conventionally, as a method of forming the protective film of a color filter, after coating and drying coating liquid containing photocurable resin, such as UV curable or ionizing radiation curable, on a to-be-coated surface, selective exposure and image development are performed by a photolithography process. After coating or drying in a predetermined pattern by a method such as printing or printing a coating liquid containing a thermosetting resin on the surface to be coated, and then heating the obtained coating layer, a cured resin layer having a predetermined pattern as a detail of a color filter is formed. It is well known to form.
[19] Moreover, as a method of forming the pixel part of a color filter, the dyeing method is mentioned, for example. In the case of the dyeing method, a water-soluble polymer material layer, which is a material for dyeing, is first formed on a glass substrate, and the pattern is formed into a desired shape by a photolithography step, and then the obtained pattern is immersed in a dyeing bath. ) To obtain a colored pattern. By repeating this three times, R, G, and B color filter layers are formed.
[20] As another method, there is a pigment dispersion method. This method first forms the photosensitive resin layer which disperse | distributed the pigment on the board | substrate, and patterns this by the photolithography process, and obtains a monochromatic pattern. Furthermore, this process is repeated three times to form color filter layers of R, G, and B.
[21] Moreover, as another method, the electrodeposition method and the method of heat-hardening resin after disperse | distributing a pigment to thermosetting resin and performing 3 times printing of R, G, and B are mentioned.
[22] When using a photocurable resin, although the coating layer is exposed to a desired pattern shape, the cured resin layer of a desired pattern can be formed in a desired position on a to-be-coated surface, but low molecular weight components, such as a monomer and a photoinitiator which are indispensable in a coating liquid, are essential. There is a risk of transferring to this liquid crystal and being contaminated to cause display defects.
[23] On the other hand, in the case of using a thermosetting resin, there is less possibility that the low molecular weight component is transferred to the liquid crystal and contaminated, compared with the UV curable resin, but it is difficult to form a complicated pattern in comparison with the photocurable resin.
[24] In addition, in the case of forming the pixel portion, in order to form three-color pixels of R, G, and B, it is necessary to repeat the same process three times in any of the methods, and the problem that the cost is high or the same process is repeated. Therefore, there exists a problem that a yield falls.
[25] As a manufacturing method of the color filter which solved these problems, the method of spraying ink on the surface of a board | substrate by the inkjet method and forming a colored layer (pixel part) is proposed (Japanese Patent Laid-Open No. 59 (1984) -75205). ).
[26] In order to form a pixel by spraying ink in accordance with an accurate pattern by an inkjet method, the linearity and stability at the time of ejecting from a recording head are calculated | required. However, if the evaporation speed of the ink is too fast, the viscosity of the ink rapidly increases at the tip of the nozzle of the recording head, causing the flight bend of the ink droplets to occur, or if intermittently ejecting it over time, it may cause clogging and cannot be discharged again.
[27] In addition, as shown in FIG. 3, when ink is wet and spread on the surface 13a around the orifice in the head 13, the ink droplet 14 discharged in the front direction Vx is wetted and spread in the direction Vy. The flight bends are caused by the drag. Thus, as the ink gets wet and spread on the surface around the orifice, the straightness of ejection is further deteriorated.
[28] When the coloring ink is sprayed onto the substrate by the inkjet method, if the drying speed is too high, the surface of the ink layer solidifies in a waved or inclined state immediately after the discharge, resulting in insufficient leveling. If the speed is too slow, it becomes difficult to dry completely by the heating process or the efficiency is poor even if the drying is possible. Therefore, in consideration of the ejection performance, an ink which is difficult to dry may be used. However, in order to completely dry the ink layer, appropriate drying property is also required.
[29] Pigments are often used as the colorant to be blended into the pixels and the black matrix of the color filter. However, if the pigment dispersibility of the ink for the color filter is poor, clogging occurs at the nozzle portion of the recording head by aggregation of the pigment particles. Therefore, when using a pigment as a coloring agent, pigment dispersibility also affects the ejection performance of an ink.
[30] Japanese Patent Application Laid-Open No. 11 (1999) -202144 discloses a filter ink containing a solvent having a boiling point of 150 ° C to 250 ° C in a proportion of 60% by weight or more, and containing at least one of glycerin, diethylene glycol or ethylene glycol as a humectant. Is disclosed. Since the ink disclosed in this publication contains a humectant, the ink is hard to dry at the tip of the nozzle of the recording head, and it is difficult to cause clogging.
[31] Japanese Unexamined Patent Application Publication No. 2000-310706 discloses a resin composition for an ink jet color filter containing a coloring agent, a binder resin, and a solvent having a boiling point of 250 ° C. or higher at normal pressure. Since the resin composition for ink jet system color filters disclosed in this publication uses a solvent having a high boiling point, it is difficult to dry the ink at the tip of the nozzle of the recording head, and it is difficult to cause clogging.
[32] However, after the ink disclosed in these publications has been discharged onto the substrate, in the process of drying the ink layer, a wetting agent or a high boiling point solvent which is difficult to dry remains until the end and it is difficult to completely dry.
[33] Moreover, when forming the detail of a color filter by thermosetting resin, it is common to use the polymerization and / or bridge | crosslinking reaction of an acid component and an epoxy component. In order to improve the strength, hardness, passivation property, etc. of a cured resin layer, it is preferable to enlarge the crosslinking density of a cured resin layer. In order to increase the crosslinking density of the epoxy-based thermosetting resin layer, the reaction point concentration of each of the acid component and the epoxy component in the coating liquid or the coating layer formed using the coating liquid is made as large as possible and / or the acid component and the epoxy component. It is desirable to make each reaction equivalent as identical as possible. However, since the acid component is poorly soluble in the organic solvent, it was difficult to coexist a large amount of the acid component in the coating liquid (in the reaction system). In addition, even if a sufficient amount of acid components suitable for the amount of the epoxy component can coexist in the coating liquid, the reactivity of the coating liquid is so high that the stability over time deteriorates, and as a result, the viscosity change (particularly, the viscosity rise) ) Tends to occur in a short time, and there is a fear that it is difficult to stably discharge the ink jet method.
[34] Japanese Patent Laid-Open No. 4 (1992) -218561 discloses a carboxylic acid block body formed by blocking a carboxyl group of a polybasic carboxylic acid with a vinyl double bond-containing compound, and capable of chemically bonding a carboxylic acid recovered from the carboxylic acid block body. A one-component thermosetting composition containing a compound containing two or more reactive functional groups is described. Since the thermosetting composition coexists in the thermosetting reaction system in the form which does not react with reactive functional groups, such as an epoxy group, using polybasic carboxylic acid as a block body, it has good storage stability, and can be used for a paint, an ink, an adhesive agent, a molded article, etc. However, in Japanese Patent Laid-Open No. 4-218561, no examination for applying the thermosetting composition to the color filter has been conducted.
[35] SUMMARY OF THE INVENTION The present invention has been accomplished in view of the above fact, and a first object thereof is to provide an ink jet ink composition for a color filter having excellent linearity and stability when discharged from a recording head, and a manufacturing method thereof.
[36] The second object of the present invention is to provide a thermosetting ink jet ink composition for color filters that can be attached in a pattern shape by using a difference in wettability to the surface of the substrate, and is excellent in straightness and stability at the time of discharge, and a manufacturing method thereof. It is to offer.
[37] Moreover, the 3rd objective of this invention is providing the method of manufacturing a color filter using the ink composition which achieves the said objective.
[1] 1 is a schematic cross-sectional view of an example of a liquid crystal panel.
[2] 2 is a schematic cross-sectional view of another example of a liquid crystal panel.
[3] 3 is a view for explaining the expansion of the wetting of the ink on the surface around the orifice and the flight bending of the ink droplets.
[4] 4 is an explanatory view of a method of producing a color filter using the ink composition of the present invention.
[5] 5 is a view for explaining another method for producing a color filter using the ink composition of the present invention.
[6] It is a figure which shows the cross-sectional shape of the cured film formed when the prebaking temperature is low.
[7] It is a figure which shows the cross-sectional shape of the cured film formed when a prebaking temperature is high.
[8] Fig. 8 is a photograph showing a state in which the ink composition (ink 1) of Example 1 is ejected by the ink jet method.
[9] 9 is a photograph showing a state in which the ink composition (ink 3) of Example 3 is discharged by an ink jet method.
[10] <Explanation of symbols for the main parts of the drawings>
[11] 1: color filter, 2: electrode substrate, 3: gap portion, 4: sealing material, 5: transparent substrate, 6: black matrix layer, 7 (7R, 7G, 7B): colored layer, 8: protective film, 9: transparent electrode Film, 10: alignment film, 11: pearl, 12: columnar spacer, 13: head, 13: surface around orifice, 14: ink drop, 15: transparent substrate, 16: black matrix layer, 17: ink repellent convex portion 18: pixel portion formation region, 19: ink jet head, 20: ink layer, 21: pixel portion, 22: protective film, 23: photocatalyst-containing layer, 24: photomask, 25: exposed portion, 26: light ray, 27a, 27b : Cured film.
[38] The ink jet ink composition for color filters according to the present invention comprises (A) an epoxy compound having two or more epoxy groups in one molecule, and (B) the following general formula (1) or (1)
[39] [Formula 1 (a)]
[40]
[41] [Formula 1 (b)]
[42]
[43] (R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each 1 to 18 carbon atoms). Y ¹ and Y ^{1 ′} are each an oxygen atom or a sulfur atom, and R ³ and R ⁴ may be bonded to each other to form a heterocycle in which Y ¹ is a hetero atom. R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and Y ^{1 ′} may be the same as R ¹ , R ² , R ³ and Y ¹ to which they correspond, respectively). It is characterized by containing as an essential component.
[44] In the present invention, the poorly soluble polybasic carboxylic acid is formed into a highly soluble carboxyl group block compound (B) by blocking (capping and protecting) the carboxyl group of the polybasic carboxylic acid, and then dissolved and dispersed in a solvent. Accordingly, the reaction point of the carboxyl group in the ink composition can coexist at high concentration with the epoxy group, and a high crosslinking density is obtained by forming and heating the ink layer using this ink composition. Moreover, a carboxyl group block compound (B) does not regenerate a carboxyl group, unless it heats more than the predetermined temperature which concerns on this compound. Therefore, although the reaction point concentration of each of the epoxy group contained in the epoxy compound (A) and the carboxyl group contained in the carboxyl group compound (B) is high, a viscosity increase occurs when being discharged from the inkjet printing head in full swing. It is difficult to be described later, and the straightness in the discharge direction from the head of the ink jet system and the stability of the discharge amount are very excellent, while in the state of the ink composition, the viscosity is maintained for a long time immediately after preparation, and also excellent in storage stability.
[45] As said epoxy compound (A), (A ') the structural unit represented by the following general formula (2) at least, and the structural unit represented by the following general formula (3)
[46] [Formula 2]
[47]
[48] (R ⁶ is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R ⁷ is a hydrocarbon group of 1 to 12 carbon atoms or-(R ⁸ X) _n -R ^9. R ⁸ is a substituted or unsubstituted C 1 to A divalent hydrocarbon group of 5, X is an oxygen atom or a sulfur atom, and R ⁹ is a C1-C12 hydrocarbon group R ⁸ and R ⁹ are bonded to each other to form a hetero atom; It may form a summon, and n is an integer of 1-10.)
[49] [Formula 3]
[50]
[51] (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
[52] It is preferable that it is a main polymer which consists of two or more glycidyl groups.
[53] The main polymer (A ') Examples of R ⁷ in the structural unit represented by the following formula (2) is - (R ⁸ X) and _n -R ^9, R ⁸ is a 2-valent hydrocarbon group having a carbon number of 1~3, X is an oxygen atom R ⁹ is an alkyl group having 1 to 3 carbon atoms, n is an integer of 1 to 5, and R ¹⁰ in the structural unit represented by the formula (3) is preferably a hydrogen atom or a methyl group.
[54] The solvent (E) to be blended as necessary in the ink composition is a main solvent, the boiling point is 180 ℃ to 260 ℃, vapor pressure at room temperature of 133 Pa (0.5 mmHg) or less, the solvent component It is preferable to contain in the ratio of 80 weight% or more with respect to whole quantity of E).
[55] A solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure of 133 Pa (0.5 mmHg) or less at room temperature (particularly in the range of 18 ° C. to 25 ° C.) has suitable drying property and evaporation property. Therefore, when a solvent containing such a solvent component at a high blending ratio is used, it does not dry rapidly at the tip of the nozzle of the recording head, so that a sudden increase in viscosity or clogging of the ink does not occur, thereby improving stability in the ejection direction and the ejection amount. Can be improved.
[56] Therefore, by using the ink composition of the present invention, the ink jet method is applied to the surface of the substrate in accordance with a predetermined pattern, so that the colored layer such as the pixel portion or the black matrix layer, in particular, the fineness of which is required for fineness, can be formed accurately and uniformly. have.
[57] Moreover, although the inkjet ink composition for color filters which concerns on this invention does not dry rapidly at the nozzle tip of an inkjet head, it has moderate dryness. Therefore, after being discharged onto the substrate, since it fuses well to the surface of the substrate and is sufficiently leveled, it can be completely dried in a relatively short time by natural drying or a general heating method. Therefore, a pattern with high uniformity can be obtained and can be dried efficiently.
[58] In addition, by selectively changing the wettability in a predetermined region of the substrate surface, an ink layer forming region having a larger ink ink relative to the surroundings is formed, and when the ink composition according to the present invention is sprayed by the ink jet method, a certain amount of The ink droplets are thrown at the correct position, and the impacted ink droplets do not stay in the impact position and are wetted and widened to every corner of the ink layer forming region, and also the ink droplets do not protrude from the boundary line with the surrounding ink repellent region. Swell Therefore, a thick cured resin layer can be formed correctly.
[59] In particular, a wettability variable layer for changing wettability in a direction in which the affinity for ink is increased by the action of the photocatalyst is formed on the substrate, and the wettability variable layer is exposed in a predetermined pattern to form an ink-inkable ink layer formation region. In this case, as the main solvent, using the standard solution presented in the wettability test specified in JIS K6768, the droplets were brought into contact with each other, and the contact angle (θ was measured after 30 seconds, and the critical surface obtained by the graph of the Jisman plot. The contact angle with respect to the surface of the test piece with a tension of 30 mN / m is 25 degrees or more, and the contact angle with the surface of the test piece with a critical surface tension of 70 mN / m determined by the same measuring method is 10 degrees or less. It is preferable to use the ink composition prepared using what is shown, and the precise and uniform pattern is obtained efficiently.
[60] Moreover, it is preferable to use the solvent which does not contain a hydroxyl group as a solvent (E). If the solvent contains a hydroxyl group, the dissolution of the blocking agent of the carboxyl group compound (B) is promoted, and the carboxyl group is likely to be expressed before the heating step. Therefore, by using the solvent which does not contain a hydroxyl group as a solvent (E), the viscosity stability of an ink composition further improves and it is excellent in the ejectability and storage stability of ink.
[61] It is preferable that the ink composition of this invention also contains the polyfunctional epoxy resin which has 2 or more of epoxy groups in 1 molecule of (C). When mix | blending a polyfunctional epoxy resin (C), an epoxy group is supplemented in an ink composition, the reaction point density | concentration of an epoxy increases, and a crosslinking density can be raised.
[62] The blending ratio of the main polymer (A '), the carboxyl group compound (B), and the polyfunctional epoxy resin (C) to be blended as necessary is 10 to 80 parts by weight of the main polymer (A') and the carboxyl group compound ( It is preferable to mix | blend 10-60 weight part of B) and 10-60 weight part of polyfunctional epoxy resins (C). In order to more accurately adjust the blending ratio in order to obtain a sufficient crosslinking density, the functional group represented by the formula (1) or formula (1) contained in the carboxyl group compound (B), and the main polymer (A ') And it is preferable to adjust so that the equivalence ratio (reaction equivalent of the functional group of reaction formula / reaction equivalent of an epoxy group) of the sum total epoxy group contained in a polyfunctional epoxy resin (C) may be in the range of 0.2-2.0.
[63] As the carboxyl group compound (B) of the ink composition, it is preferable to use a monocyclic aromatic carboxylic acid derivative represented by the following formula (5), and specifically, trimesic acid (benzene-1,3,5-tricarboxylic acid) and / Or the block body of trimellitic acid (benzene-1,2,4-tricarboxylic acid) can be illustrated.
[64] [Formula 5]
[65]
[66] (F3 is a functional group represented by formula (1) or formula (1), and m is an integer of 2 or more.
[67] The ink composition may also contain a catalyst selected from the group consisting of (D) a thermal latent catalyst exhibiting activity upon heat curing, and preferably (D ') a halogen-free acidic catalyst. desirable. Mixing these catalysts promotes the thermosetting reaction between the acid and the epoxy at the time of thermal curing, thereby improving the hardness and heat resistance of the cured resin layer.
[68] It is preferable that the weight average molecular weight of the main polymer (A ') contained in the said ink composition is 10,000 or less. If the weight average molecular weight of the main polymer (A ') is too large, the viscosity is likely to rise, and there is a fear that the stability of the discharge amount and the straightness of the discharge direction when discharged from the recording head are deteriorated, and the stability of the long-term storage is deteriorated.
[69] Moreover, when the weight average molecular weight of the said main polymer (A ') is made into 10,000 or less, since the intensity | strength and hardness of a cured resin layer fall easily, four or more polyfunctional epoxy resins are mix | blended with an ink composition, and sufficient crosslinking density is carried out. It is desirable to increase.
[70] A pigment can be mix | blended with the said ink composition, and coloring layers, such as a pixel part and a black matrix layer, can be formed. Although the fineness is especially required for colored layers, such as a pixel part and a black matrix layer, the ink composition of this invention can ensure sufficient dispersibility even when a pigment is mix | blended and discharged stably from the head of an inkjet system. It is possible to accurately form a fine colored layer.
[71] The method for producing an ink jet ink composition for a color filter according to the present invention includes a pigment and, if necessary, a pigment dispersant as a main solvent, a boiling point of 180 ° C. to 260 ° C., and a solvent component having a vapor pressure of 133 Pa (0.5 mmHg) or less at room temperature. A pigment dispersion obtained by mixing with a dispersion preparation solvent to prepare a pigment dispersion, (A) an epoxy compound having two or more epoxy groups in one molecule, (B) the following formula (a) or formula (b)
[72] [Formula 1 (a)]
[73]
[74] [Formula 1 (b)]
[75]
[76] (R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each an organic group having 1 to 18 carbon atoms). , Y ¹ and Y ^{1 'are} independently an oxygen atom or a sulfur atom. R ³ and R ⁴ may form a heterocyclic ring, which hetero atom of Y ¹ bonded to each other. ^{Further, R 1', R 2 '} , R ^{3 '} and Y ^1' may be the same as R ¹ , R ² , R ³ and Y ¹ to which they respectively correspond.) A carboxyl group compound having two or more functional groups and other components, if necessary, It is characterized by mixing with the newly prepared main solvent and adjusting the blending ratio of the main solvent to the total amount of the solvent to 80% by weight or more.
[77] When a pigment is directly added to the whole solvent and stirred and mixed with other components, such as a binder component, in many cases, a pigment cannot fully be disperse | distributed in a solvent. Therefore, when mix | blending a pigment with the inkjet ink composition for color filters of this invention, the solvent which is excellent in the dispersibility and dispersion stability of a pigment is normally prepared, and a pigment is put together with a dispersing agent therein and a pigment dispersion is prepared. . And the obtained pigment dispersion can be made into the ink composition which concerns on this invention by mixing with the component other than a pigment in the solvent which consists mostly of a main solvent, or consists only of a main solvent.
[78] Hereinafter, the present invention will be described in detail. The ink jet ink composition for color filters according to the present invention,
[79] (A) an epoxy compound having two or more epoxy groups in one molecule, and
[80] (B) Formula 1 (a) or Formula 1 (b)
[81] [Formula 1 (a)]
[82]
[83] [Formula 1 (b)]
[84]
[85] (R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each an organic group having 1 to 18 carbon atoms). , Y ¹ and Y ^{1 'are} independently an oxygen atom or a sulfur atom. R ³ and R ⁴ may form a heterocyclic ring, which hetero atom of Y ¹ bonded to each other. ^{Further, R 1', R 2 '} , R ^{3 '} and Y ^1' may contain, as essential components, a carboxyl group compound having at least two functional groups represented by R ¹ , R ² , R ³ and Y ¹ to which they respectively correspond. do.
[86] (Binder system)
[87] In the present invention, an epoxy compound (A) having two or more epoxy groups in one molecule, and a carboxyl group compound (B) having two or more functional groups represented by formula (1) or formula (1) as essential components A binder system is used. This binder system has excellent storage stability despite the high concentration of reaction points of each of the carboxyl group and the epoxy group. Therefore, it is difficult to increase the viscosity when being discharged from the inkjet recording head in the middle, and can be stably discharged. Flight bending and clogging of the recording head are less likely to occur. Moreover, it is excellent also in long-term storage property.
[88] (A) The epoxy compound which has 2 or more epoxy groups in 1 molecule (henceforth (A component) or an epoxy compound (A)) has 2 or more epoxy groups, Preferably it is 2-50 pieces, More preferably, 2 It is an epoxy compound (including what is called an epoxy resin) which has -20 in 1 molecule. What is necessary is just to have a structure which has an oxirane ring structure, and an epoxy group can represent glycidyl group, an oxyethylene group, an epoxy cyclohexyl group, etc., for example. As an epoxy compound (A), the well-known polyhydric epoxy compound which can harden | cure with a carboxylic acid is mentioned, Such an epoxy compound is, for example, Masaki Jinzo "Epoxy resin handbook" "It is widely disclosed in Nikkan Kogyo Shobun Shakan (Showa 62), etc., and these can be used. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydrokinone type epoxy resin, naphthalene type epoxy resin, biphenyl type Epoxy resin, fluorene type epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylrolethane type epoxy resin, dicyclopenta Dienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A containing polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glyox A well type epoxy resin, an alicyclic epoxy resin, a heterocyclic epoxy resin, etc. are mentioned.
[89] As an epoxy compound (A), it is preferable to use the main polymer (A ') comprised from the structural unit represented by the following general formula (2) and the structural unit represented by the following general formula (3), and having 2 or more glycidyl groups. .
[90] [Formula 2]
[91]
[92] (R ⁶ is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R ⁷ is a hydrocarbon group of 1 to 12 carbon atoms or-(R ⁸ X) _n -R ^9. R ⁸ is a substituted or unsubstituted C 1 to A divalent hydrocarbon group of 5, X is an oxygen atom or a sulfur atom, and R ⁹ is a C1-C12 hydrocarbon group R ⁸ and R ⁹ are bonded to each other to form a hetero atom; It may form a summon, and n is an integer of 1-10.)
[93] [Formula 3]
[94]
[95] (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
[96] The structural unit represented by the formula (2) is derived from the monomer represented by the formula (8).
[97] [Formula 8]
[98]
[99] (R ⁶ and R ⁷ are the same as in the general formula (2).)
[100] The monomer represented by the formula (8) is used to impart sufficient hardness and transparency to the cured coating formed from the ink jet ink composition of the present invention. In formula (8), R ⁷ is a C1-C12 hydrocarbon group or-(R ⁸ X) _n -R ⁹ . Here, R <^8> is a substituted or unsubstituted C1-C5 bivalent hydrocarbon group, X is an oxygen atom or a sulfur atom, R <^9> is a C1-C12 hydrocarbon group. R ⁸ and R ⁹ may be bonded to each other to form a heterocycle in which X is a hetero atom. In addition, n is an integer of 1-10. R ⁷ may be any linear aliphatic, alicyclic or aromatic hydrocarbon group, and additional structures such as double bonds, side chains of hydrocarbon groups, side chains of spiro rings, and rings ( Vi) may contain a crosslinked hydrocarbon group and the like. Further, R ⁷ is - (R ⁸ X) _n -R ⁹ if, plural repeating units - (R ⁸ X) -, the carbon atoms or may be a mixture of different groups are divalent hydrocarbon.
[101] As a monomer represented by the said Formula (8), specifically, methyl (meth) acrylate, methyl (meth) acrylate, i-propyl (meth) acrylate, n-propyl (meth) acrylate, i-butyl (meth) Acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) Acrylate, cyclohexyl (meth) acrylate, para-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Phenyl (meth) acrylate etc. can be illustrated, Moreover, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, methoxyphenyl (meth) Acrylate etc. can be illustrated. Here, (meth) acrylate means that any of acrylate or methacrylate may be sufficient.
[102] In the formula (8), R ⁶ is preferably hydrogen or a methyl group, and R ⁷ is preferably-(R ⁸ X) _n -R ⁹ (herein, particularly preferred-(R ⁸ X) _n -R ⁹ , R ⁸ Is a substituted or unsubstituted divalent or higher hydrocarbon group having 1 to 3 carbon atoms, X is an oxygen atom, R ⁹ is a hydrocarbon group having 1 to 5 carbon atoms, and n is an integer of 1 to 5). A methoxy polyethyleneglycol group, especially a methoxyethyl group is preferable. As a preferable thing in the monomer represented by the said Formula (8), a methoxy ethyl acrylate (MEA) and a methoxy polyethylene glycol mono (meth) acrylate are mentioned specifically ,.
[103] The structural unit represented by the formula (3) in the main polymer (A ') is derived from the monomer represented by the following formula (9).
[104] [Formula 9]
[105]
[106] (R ¹⁰ is the same as in Formula 3.)
[107] The monomer represented by the formula (9) is used to introduce an epoxy group (reaction point of epoxy) into the main polymer (A '). The ink composition containing the main polymer (A ') is excellent in storage stability, and it is difficult to generate a viscosity increase during storage and discharge operation, but one of the reasons is presumed that the epoxy group in the formula (3) or (9) is glycidyl group. do. When an alicyclic epoxy acrylate is used instead of the monomer represented by General formula (9), the viscosity of the coating liquid for protective films will rise easily.
[108] In formula (9), preferred as R ¹⁰ are hydrogen or a methyl group. As a monomer represented by General formula (9), specifically, glycidyl (meth) acrylate can be illustrated, A glycidyl methacrylate (GMA) is especially preferable.
[109] The main polymer (A ') may be a random copolymer, a block copolymer, or a block copolymer. In addition, the main polymer (A ') may include main chain structural units other than the general formula (2) or the general formula (3) as long as the performance required for each detail of the color filter, for example, hardness and transparency can be secured. . Specifically as such a monomer, acrylamide, acrylonitrile, styrene, etc. can be illustrated.
[110] The content of the structural unit of the general formula (2) and the structural unit of the general formula (3) in the main polymer (A ') is the input weight ratio of the monomer which derives the structural unit of the general formula (2) and the monomer which derives the structural unit of the general formula (3) Monomer: Monomer which derives general formula (3)), It is preferable to exist in the range of 10: 90-90: 10. When the amount of the structural unit of the formula (2) is excessive, there is a fear that the reaction point of curing is reduced and the crosslinking density is low. On the other hand, when the amount of the structural unit of the formula (3) is excessive, the bulky skeleton is reduced and cured. There is a risk of shrinkage.
[111] Glass transition temperature (Tg) of main polymer (A ') is 70 degrees C or less, especially 30 degreeC, in order to prevent the crack at the time of drying and thermosetting (baking) the coating film of the ink composition concerning this invention. It is preferable that it is the following. The main polymer (A ') having such a Tg is a monomer represented by the formula (8), which is a structural unit of the polymer, having R ⁶ and R ⁷ of the above preferred structure, that is, R ⁶ is hydrogen or a methyl group, and R ⁷ In this-(R ⁸ X) _n -R ⁹ (wherein particularly preferred-(R ⁸ X) _n -R ⁹ , R ⁸ is a substituted or unsubstituted divalent or higher hydrocarbon group having 1 to 3 carbon atoms, X is an oxygen atom, R ⁹ is a C1-C5 hydrocarbon group, and n is an integer of 1-5. Among the main polymer (A ') whose Tg is 70 degrees C or less, as a monomer represented by General formula (8), a methoxy ethyl acrylate (MEA) and a methoxy poly (n) ethylene glycol monomethacrylate [as n <2>, PME-100, and n ≒ 9, Brenma PME-400; All synthesize | combined using bulky monomers, such as those made by Nippon-KKK Co., Ltd., are considered to have particularly high flexibility of the polymer, and are particularly effective for crack prevention.
[112] The reason why a crack can be prevented by using the main polymer (A ') of Tg of 70 degrees C or less is as follows. That is, the coating film of the ink composition according to the present invention is usually a desired cured film by drying by evaporating the solvent in the pre-baking step, and then performing post-baking and thermosetting, but in the pre-baking step as described below. By carrying out drying at a relatively high temperature, when the film thickness is uniform or if there is irregularities in the base, a dry film having a high flatness is obtained, and it is possible to form a cured film having a high flatness through subsequent postbaking. However, when prebaking is performed at a high temperature, the drying is too fast, so that the film reduction (volume reduction of the coating film) proceeds rapidly and cracks are likely to occur. On the other hand, the coating film of the ink composition which mix | blended the main polymer (A ') whose Tg is 70 degrees C or less has the inside of a coating film even when the film | membrane reduction of a coating film advances rapidly at the time of baking, especially at the time of the said prebaking at high temperature. It is assumed that it has the flexibility to absorb the distortion which arises, and it is hard to produce a crack. Therefore, it is especially preferable from a viewpoint of crack prevention and shape or film thickness control at the time of manufacturing cured films, such as a pixel.
[113] Moreover, when the weight average molecular weight of a main polymer (A ') is shown by the polystyrene conversion weight average molecular weight, it is preferable that it is 10,000 or less, and it is especially preferable to exist in the range of 2,000-4,000. If the molecular weight of the main polymer (A ') is too small, physical properties such as strength and solvent resistance required for the cured resin layer as details of the color filter tend to be insufficient. It is liable to occur, which may deteriorate the stability of the discharge amount and the straightness of the discharge direction when discharging from the recording head, or deteriorate the stability of the long-term storage.
[114] As the main polymer (A '), it is particularly preferable to use a glycidyl methacrylate (GMA) / methoxyethyl acrylate (MEA) copolymer having a polystyrene reduced weight average molecular weight in the range of 2,000 to 4,000. The GMA / MEA copolymer may contain other monomer components as long as the object of the present invention can be achieved.
[115] As a synthesis example of a main polymer (A '), the solvent which does not contain a hydroxyl group is put into the four neck flask provided with a thermometer, a reflux condenser, an agitator, and a dropping funnel, for example, and it is 140 degreeC, stirring. Increase the temperature. The use of a solvent containing no hydroxyl group is intended to avoid decomposition of the epoxy group during the synthesis reaction. Subsequently, the mixture (dropping component) of the monomer represented by the said Formula (8), the monomer represented by the said Formula (9), and the composition which combined the other monomer as needed, and a polymerization initiator are carried out isotropically from the dropping funnel over 2 hours. ) Dropping off. After completion of dropping, the temperature was dropped to 110 ° C, a catalyst was added, and the reaction was terminated when the temperature at 110 ° C was maintained for 2 hours, thereby obtaining a main polymer (A ').
[116] The carboxyl group block compound (B) having two or more functional groups represented by Formula 1 (a) or Formula 1 (b) is a curing agent of the main polymer, and reacts a compound having a vinyl double bond with a polybasic carboxylic acid. It is a cap body which blocked (protected) a carboxy group according to this.
[117] Among the carboxyl group compounds (B), compounds having two or more functional groups represented by the general formula (1) include a vinyl ether compound, a vinylthioether compound, an oxygen atom, or a sulfur atom represented by the following general formula (10) in the polybasic carboxylic acid: It is obtained by reacting the heterocyclic compound which has a vinyl double bond as a hetero atom.
[118] [Formula 10]
[119]
[120] (R ¹ , R ² , R ³ , R ⁴ , and Y ¹ are the same as in the general formula (1).)
[121] R <^1> , R <^2> and R <^3> in the said Formula (1) and Formula (10) are a hydrogen atom or an organic group, such as a C1-C18 alkyl group, an aryl group, and an alkali group, respectively, and R <^4> is C1-C18 It is an organic group, such as an alkyl group, an aryl group, and an alkali group of these, These organic groups may have a suitable substituent, and R <^3> and R <^4> may combine with each other, and may form the heterocycle which makes Y <^1> a hetero atom.
[122] Specific examples of the compound represented by the formula (10) include, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, Aliphatic vinyl ether compounds, such as 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether, and the aliphatic vinyl thioether compound corresponding to these, 2, 3- dihydrofuran, 3, 4- dihydrofuran, 2, 3-di Hydro-2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran- Cyclic vinyl ether compounds such as 2-one, 3,4-dihydro-2-ethoxy-2H-pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate and cyclic vinylthioethers corresponding thereto Compounds and the like.
[123] As the compound represented by the formula (10), primary alkyl vinyl ethers having a higher dissociation temperature than secondary and tertiary alkyl vinyl ethers, in particular normal propyl vinyl ether (dissociation temperature of about 140 ° C.) and / or normal butyl vinyl ether (dissociation temperature of about 1600 degreeC), the crack at the time of drying of a coating film and thermosetting (baking) can be prevented.
[124] The reason why a crack can be prevented by using the carboxyl group compound (B) by primary alkyl vinyl ether is as follows. That is, the coating film of the ink composition according to the present invention is usually a desired cured film by drying by evaporating the solvent in the pre-baking step, and then performing post-baking and thermosetting, but in the pre-baking step as described below. By carrying out drying at a relatively high temperature, when the film thickness is uniform or if the base has irregularities, a dry film having a high flatness is obtained, and a cured film having a high flatness can be formed through subsequent post-baking. However, when a coating film is formed using an ink composition containing a carboxyl group compound (B) having a low dissociation temperature of vinyl ether, and a high temperature prebaking is carried out, the drying is too fast and the film decreases rapidly (the volume of the coating film) rapidly. In parallel with the progression, since the dissociation temperature of the vinyl ether is reached in this prebaking step, and the thermosetting reaction of the epoxy compound also proceeds, distortion occurs inside the coating film, causing cracks.
[125] On the other hand, the coating film of the ink composition which mix | blended the carboxyl group compound (B) by the primary alkyl vinyl ether with a dissociation temperature higher than secondary and tertiary alkyl vinyl ether is a coating film because the heating temperature at the time of the said prebaking is high temperature. Even if the film reduction proceeds rapidly, since simultaneous progress of the thermosetting reaction can be avoided, it is estimated that the flexibility to absorb the distortion generated inside the coating film is maintained, and it is difficult to cause cracks. Then, after the prebaking is made into a dry film that is flat and free of cracks, the thermosetting reaction can be selectively performed by initiating dissociation of the primary alkyl vinyl ether by further raising the heating temperature in the postbaking step. Therefore, it is especially preferable from a viewpoint of crack prevention and shape or film thickness control at the time of manufacturing cured films, such as a pixel.
[126] Of the carboxyl group compounds (B), compounds having two or more functional groups represented by the general formula (1) are obtained by reacting a polybasic carboxylic acid with a divinylether compound or a divinylthioether compound represented by the following general formula (11). Lose.
[127] [Formula 11 ]
[128] (R ¹ , R ² , R ³ , Y ¹ , R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , Y ^{1 ′} and R ⁵ are the same as in Formula 1 (b).)
[129] In the molecule | numerator of the divinyl ether compound or the divinyl thioether compound represented by the said Formula (11), two vinyl structures which can protect a carboxy group exist. Therefore, when a polyvinyl carboxylic acid, especially a dicarboxylic acid, is reacted with the divinyl ether compound or the divinyl thioether compound represented by the above formula (11), the functional group represented by the formula (1) as a main chain structural unit A carboxyl group block compound (B) of the polymer type which has 2 or more of is obtained.
[130] As a compound represented by the said Formula (11), 1, 4- cyclohexane dimethanol divinyl ether, 1, 4- cyclohexanediol divinyl ether, 1, 9- nonane diol divinyl ether, 1, 6- hexanediol divinyl Ether, 1, 4- cyclodiol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, bisphenol A divinyl ether Water addition bisphenol A divinyl Divinyl ether compounds, such as ether, and the divinyl thioether compound corresponding to these are mentioned.
[131] Examples of the polybasic carboxylic acid protected by the vinyl double bond-containing compound represented by the formula (10) or (11) include succinic acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, azelaic acid and sebacic acid. Aliphatic polycarboxylic acids such as decamethylene dicarboxylic acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; Alicyclic polycarboxylic acids such as tetrahydrophthalic acid and hexahydrophthalic acid; And polymer carboxylic acids such as polyester resins having two or more carboxyl groups in one molecule, acrylic resins, and maleated polybutadiene resins; Etc. can be mentioned.
[132] As other polybasic carboxylic acid, it is (1) the method of half-esterifying the polyol and acid anhydride which have two or more 1 molecular contact hydroxyl groups, and (2) two or more 1 molecular contact isocyanate groups, for example. A method of adding a polyisocyanate compound having a hydroxycarboxylic acid or an amino acid with a polyisocyanate compound, (3) a method of homopolymerizing or copolymerizing a carboxyl group-containing α, β-unsaturated monomer with another α, β-unsaturated monomer, and (4) a polycarboxylate terminal What is obtained by the method of synthesize | combining ester resin, etc. are mentioned.
[133] In these methods, as the polyol, for example, ethylene glycol, 1,2- and 1, 3-propylene glycol, or the like can be used. As the acid anhydride, for example, succinic acid, glutaric acid, adipic acid, Anhydrides of polyhydric carboxylic acids can be used, and as polyisocyanate compounds, for example, p-phenylene diisocyanate, biphenyl diisocyanate and the like can be used, and as hydroxycarboxylic acid, for example, citric acid and hydroxypivalic acid Etc. can be used, for example, DL-alanine, L-glutamic acid or the like can be used as the amino acid, and acrylic acid, methacrylic acid, itaconic acid or the like can be used as the carboxyl group-containing α, β-unsaturated monomer. As another α, β-unsaturated monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) a You can use the relay agent and the like. Moreover, the polyester resin of a carboxyl group terminal can be easily formed with respect to a polyhydric alcohol according to the synthesis | combining method of normal polyester resin under polybasic acid excess.
[134] In general, when the carboxyl group is protected (blocked) by reacting the polybasic carboxylic acid with a vinyl double bond-containing compound represented by Formula 10 or Formula 11 at a temperature of room temperature to 100 ° C. in the presence of an acid catalyst, A carboxy group block compound (B) having two or more functional groups represented by (a) or formula (1) is obtained. The polybasic carboxylic acid preferably has about 2 to about 4 carboxyl groups in one molecule. In order to introduce a large amount of carboxyl groups in the carboxyl group compound (B) to increase the reaction point density of the acid, the polybasic carboxylic acid preferably has an acid equivalent of 50 g / mol or more. Moreover, in order to make storage stability (viscosity stability) of an ink composition favorable, it is preferable that the polystyrene conversion weight average molecular weight of a carboxy group block compound is 10,000 or less.
[135] Specific examples of the carboxyl group compound (B) include aromatic carboxylic acid derivatives represented by the following general formula (4).
[136] [Formula 4]
[137]
[138] (The cyclic structure represented by A is an aromatic hydrocarbon ring, F3 is a functional group represented by the formula (1) or (1), and n is an integer of 2 or more.)
[139] The aromatic carboxylic acid derivative represented by the formula (4) is obtained by blocking the aromatic polybasic carboxylic acid represented by the following formula (6).
[140] [Formula 6]
[141]
[142] (The cyclic structure represented by A and n are the same as above.)
[143] Examples of the aromatic polybasic carboxylic acid represented by the formula (6) include isophthalic acid, terephthalic acid, trimesic acid (benzene-1,3,5-tricarboxylic acid) and trimellitic acid (benzene-1,2,4-tricarboxylic acid ), 2,6-naphthalenedicarboxylic acid, pyromellitic acid, and the like.
[144] Among the aromatic carboxylic acid derivatives represented by the general formula (4), the monocyclic aromatic carboxylic acid derivatives represented by the following general formula (5) is particularly preferable.
[145] [Formula 5]
[146]
[147] (F3 is the same as that of Formula 4. In addition, m is an integer of 2 or more.)
[148] Monocyclic aromatic carboxylic acid derivative represented by General formula (5) is obtained by blocking monocyclic aromatic polybasic carboxylic acid represented by following General formula (7).
[149] [Formula 7]
[150]
[151] m is the same as above.
[152] As the monocyclic aromatic carboxylic acid represented by the formula (7), isophthalic acid, terephthalic acid, trimesic acid and trimellitic acid among those exemplified in the formula (6) are preferred, and among them, trimesic acid and trimellitic acid having three carboxyl groups are preferable. Do. When glycidyl methacrylate is used as the epoxy component (constituent unit of formula (2)) in the main polymer (A '), excellent coating film hardness is obtained by using trimellitic acid, which is particularly preferable.
[153] In this invention, it is preferable to add the polyfunctional epoxy resin which has 2 or more epoxy groups to 1 ink molecule (C) further to an inkjet ink composition. Although epoxy group (glycidyl group) is introduce | transduced into the main polymer (A ') by the structural unit represented by General formula (3), there is a limit to the amount of epoxy which can be introduce | transduced into the molecule | numerator of main polymer (A'). When the polyfunctional epoxy resin (C) is added to the ink composition, the epoxy group is replenished in the ink composition to increase the reaction point concentration of the epoxy, thereby increasing the crosslinking density.
[154] Among polyfunctional epoxy resins, in order to increase the crosslinking density of an acid-epoxy reaction, it is preferable to use the epoxy resin which has four or more epoxy groups in 1 molecule. In particular, when the weight average molecular weight of the main polymer (A ') is set to 10,000 or less in order to improve the ejectability from the ink jet printing head, the strength and hardness of the cured resin layer tend to be lowered. It is preferable to mix | blend tetrafunctional or more than polyfunctional epoxy resin with an ink composition, and to fully raise a crosslinking density.
[155] The polyfunctional epoxy resin (C) is not particularly limited as long as it contains two or more epoxy groups in one molecule, and examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, and bisphenol S. Type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolak type epoxy resin, allocresol novolak type epoxy resin, trishydr Oxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylrolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, water addition bisphenol A type epoxy resin, bisphenol A containing nucleus polyol type epoxy resin, Polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glyoxal Type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, etc. can be used.
[156] More specifically, bisphenol A type epoxy resins, such as brand name Epicoat 828 (made by Japan Epoxy Resin Corp.), bisphenol F type epoxy resins, such as brand name YDF-175S (made by Toyo Chemical Co., Ltd.), brand name YDB-715 (東 都 化成) Bisphenol A type epoxy resins, such as a brominated bisphenol A type epoxy resin, the brand name EPICLON EXA1514 (made by Dainippon Ink & Chemicals Co., Ltd.), hydroquinone type epoxy resins, such as brand name YDC-1312 (made by Toyo Chemical Co., Ltd.), brand names Naphthalene type epoxy resins, such as EPICLON EXA4032 (made by Dainippon Ink & Chemicals Co., Ltd.), biphenyl type epoxy resins, such as brand name Epicoat YX4000H (made by Japan Epoxy Resin Corp.), brand name Epicoat 157S70 (made by Japan Epoxy Resin Corp.) Bisphenol-A novolak-type epoxy resins, such as phenol novolak-type epoxy resins, such as brand name YDPN-638 (made by Tosho Chemical Co., Ltd.), cresol novolak-type epoxy resins, such as brand name YDCN-701 (made by Totoga Corporation), EPICLON Dicyclopentadiene phenol type epoxy resins, such as HP-7200 (made by Dainippon Ink & Chemicals Co., Ltd.), trishydroxy phenylmethane type epoxy resins, such as brand name Epicoat 1032H60 (made by Japan Epoxy Resin Corp.), brand name VG310lM80 (Mitsui Such as trifunctional epoxy resins such as Chemical Corp.), tetraphenylolethane type epoxy resins such as trade name Epicoat 1031S (manufactured by Japan Epoxy Resin Corp.), and brand name Denacol EX-411 (manufactured by Nagase Chemical Co., Ltd.). Glycidyl ester type epoxy resins, such as water-added bisphenol-A epoxy resin, such as a 4-functional epoxy resin, brand name ST-3000 (made by Tosho Chemical Co., Ltd.), brand name Epicoat 190P (made by Japan Epoxy Resin Corp.), brand name YH Glycidylamine type epoxy resins such as -434 (manufactured by Toyo Chemical Co., Ltd.), glyoxal type epoxy resins such as brand name YDG-414 (manufactured by Toyo Chemical Co., Ltd.), trade name Epoide GT-401 (manufactured by Daisen Chemical Industries Ltd.) Alicyclic polyfunctional epoxy resins, such as Receiving dill isocyanate (TGlC) and the like can be given complex cyclic epoxy resins such as. If necessary, a brand name Neoto E (manufactured by Toyo Chemical Co., Ltd.) or the like can be mixed as the epoxy reactive diluent.
[157] Among these polyfunctional epoxy resins, cresol novolak-type epoxy resins such as bisphenol A novolac-based epoxy resins such as Epicoat 157S70 (manufactured by Japan Epoxy Resin Corp.) and trade name YDCN-701 (manufactured by Toyo Chemical Co., Ltd.). Is particularly preferred.
[158] In order to improve the hardness and heat resistance of the cured resin layer, a catalyst capable of promoting the heat curing reaction between the acid and the epoxy may be added to the ink jet ink composition of the present invention. As such a catalyst, a thermal latent catalyst (hereinafter referred to as component (D) or a thermal latent catalyst (D)) that exhibits activity during heat curing (D) can be used.
[159] The heat latent catalyst (D), when heated, exhibits catalytic activity, accelerates the curing reaction, imparts good physical properties to the cured product, and is added as necessary. It is preferable that this heat latent catalyst (D) starts to express catalytic activity after reaching the temperature of 60 degreeC or more, As such, the compound which neutralized protonic acid by the Lewis base, and the compound which neutralized Lewis acid by the Lewis base And mixtures of Lewis acid and trialkyl phosphate, sulfonic acid esters, onium compounds, and the like, and various compounds such as those described in Japanese Patent Application Laid-Open No. 4-218561 can be used. Specifically, (a) neutralize halogenocarboxylic acids, sulfonic acids, monophosphoric acid and diesters with various amines such as ammonia, monomethylamine, triethylamine, pyridine, ethanolamine, or trialkylphosphine; (B) compounds obtained by neutralizing Lewis acids such as BF ₃ , FeCl ₃ , SnCl ₄ , AlCl ₃ , ZnCl ₂ with the above-mentioned Lewis base, ( _c ) methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and primary alcohols And ester compounds with secondary alcohols, (d) primary alcohols, phosphate monoester compounds of secondary alcohols, and phosphate diester compounds. Examples of the onium compound include an ammonium compound [R ₃ NR ′] ⁺ X ⁻ , a sulfonium compound [R ₃ SR ′] ⁺ X ⁻ , an oxonium compound [R ₃ OR ′] ⁺ X ⁻ , and the like. And wherein R and R 'are groups such as alkyl, alkenyl, allyl, alkoxy and the like.
[160] In addition, the thermal latent catalyst (D) is preferably a (D ') halogen-free acidic catalyst (hereinafter referred to as a (D') component or a halogen-free acidic catalyst (D ')) in terms of liquid crystal contamination. Do. Specifically as a halogen-free acidic catalyst (D '), Nofcure LC-1 and Nofcure LC-2 (both a brand name and a Japanese oil and fat company make) can be illustrated.
[161] (Pigment)
[162] When forming the colored layer like a pixel part and a black matrix layer using the inkjet ink composition which concerns on this invention, a pigment or other coloring agent is mix | blended in an ink composition.
[163] The pigment as a coloring agent can be used arbitrarily among the organic coloring agent and an inorganic coloring agent according to the color calculated | required, such as R, G, and B of a pixel part. As the organic colorant, for example, dyes, organic pigments, natural dyes and the like can be used. Moreover, as an inorganic coloring agent, an inorganic pigment, a extender pigment, etc. can be used, for example. Among these, organic pigments are preferably used because of their high color development and high heat resistance. As the organic pigment, for example, a compound classified as a pigment in a color index (CI; issued by The Society of Dyers and Colourists, Inc.), specifically, is given the following color index (CI) number. It can be mentioned.
[164] CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment CIment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Kinico 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow l19, CI Pigment Yellow 120, CI Pigment Yellow 126 CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175;
[165] CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Cement Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI pigment orange 64, CI pigment orange 71, CI pigment non orange 73; C.I. Pigment Violet 1, C.I.Pigment Violet 19, C.I.Pigment Violet 23, C.I.Pigment Violet29, C.I.Pigment Violet 32, C.I.Pigment Violet 36, C.I.Pigment Violet 38;
[166] CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Cement Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Red 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Cement Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63 : 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97, CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113 CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 15l, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Cement Red l90, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI pigment red 255, CI pigment red 264, CI pigment red 265;
[167] C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I.Pigment Blue 60; C.I. pigment green 7, C.I. pigment green 36; C.I. pigment brown 23, C.I. pigment brown 25; Pigment Black 1, Pigment Black 7.
[168] Specific examples of the inorganic pigment or extender pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc sulfur, 43 iron oxide [red iron oxide (III)], cadmium red, and ultramarine blue. , Blue green, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. In this invention, a pigment can be used individually or in mixture of 2 or more types.
[169] When forming the pattern of a light shielding layer using the ink composition of this invention on the board | substrate of a color filter, the black pigment with high light shielding property is mix | blended in an ink composition. As black pigment with high light-shielding property, it is preferable to use inorganic coloring agents, such as carbon black and 43 iron oxides, or organic coloring agents, such as cyanine black, for example.
[170] (Other ingredients)
[171] 1 type (s) or 2 or more types of other additives can be mix | blended with the inkjet ink composition for color filters of this invention as needed. As such an additive, the following can be illustrated.
[172] a) dispersant
[173] When mix | blending a pigment with an ink composition, a dispersing agent is mix | blended with an ink composition as needed in order to disperse | distribute the said pigment favorably. As the dispersant, for example, surfactants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based compounds can be used. Among the surfactants, polymer surfactants (polymer dispersants) as illustrated below are preferable.
[174] Namely, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octyl petyl ether and polyoxyethylene nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid-modified polyesters; Polymeric surfactants, such as tertiary amine modified polyurethanes, are used preferably.
[175] b) Dispersion adjuvant: For example, blue pigment derivatives, such as a copper phthalocyanine derivative, a yellow pigment derivative, etc.
[176] c) fillers: for example glass, alumina and the like.
[177] d) Adhesion promoters: for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Etc.
[178] e) antioxidants: for example, 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and the like.
[179] f) UV absorbers: for example, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
[180] g) anti-aggregation agents: for example, sodium polyacrylate, various surfactants and the like.
[181] h) Leveling agents: For example, commercially available silicone-based, polyalkylene ether-based, fatty acid ester-based, special acrylic polymers and the like.
[182] (Mixture ratio of solids)
[183] In order to design the ink composition which has both the performance required as a color filter and the performance required as an inkjet ink, the compounding ratio of each said material is determined.
[184] The blending ratio of the main polymer (A '), the carboxyl group compound (B), and the polyfunctional epoxy resin (C) to be blended as necessary is 10 to 80 parts by weight of the main polymer (A') and the carboxyl group block as the weight ratio. It is preferable to mix | blend a compound (B) 10-60 weight part and a polyfunctional epoxy resin (C) in the ratio of 10-60 weight part, 20-60 weight part of main polymer (A '), and a carboxy group block compound It is especially preferable to mix | blend 20-50 weight part of (B) and 20-50 weight part of polyfunctional epoxy resin (C), and 30-40 weight part of main polymer (A ') and a carboxy group block compound It is most preferable to mix | blend 35-45 weight part of (B) and 25-35 weight part of polyfunctional epoxy resin (C).
[185] In order to obtain a sufficient crosslinking density, in the case of more precisely adjusting the blending ratio, the functional group represented by the formula (1) or formula (1) contained in the carboxyl group compound (B), and the main polymer (A ') And it is preferable to adjust so that the equivalence ratio (reaction equivalent of the functional group of Formula 1 / reaction equivalent of an epoxy group) of the sum total epoxy group contained in a polyfunctional epoxy resin (C) may be in the range of 0.2-2.0, and it is the range of 0.5-1.2 It is especially preferable to adjust to If the equivalent ratio (reaction equivalent / functional equivalent of the functional group of the formula (1) or formula (1)) is less than 0.2, the reaction may be slow, resulting in poor curing, and on the other hand, if the equivalent ratio exceeds 2.0, Since the amount of residual epoxy groups decreases, there is a fear that the adhesiveness is remarkably lowered.
[186] Moreover, in order to provide sufficient adhesiveness, strength, and hardness to a cured resin layer, the main polymer (A '), a carboxy group block compound (B), and a polyfunctional epoxy which occupy the solid content whole quantity of the ink composition containing a pigment and other components. It is preferable to make the total ratio of resin (C) into 50 weight% or more. Here, solid content of the ink composition for specifying a compounding ratio contains all the components except a solvent, and also a liquid polyfunctional epoxy resin etc. are contained in solid content.
[187] The heat latent catalyst (D) is usually about 0.01 to 10.0 parts by weight based on 100 parts by weight of the total of the main polymer (A '), the carboxyl group compound (B), and the polyfunctional epoxy resin (C). Blend in proportions.
[188] When mix | blending a pigment in an ink composition, it is mix | blended in the ratio of 10-40 weight% normally, Preferably it is about 20-30 weight% with respect to solid content whole quantity of an ink composition. When there are too few pigments, the coating film formed by apply | coating an ink composition to predetermined | prescribed film thickness (typically 0.1-2.0 micrometers) may not transmit the light which has desired color, sufficient density | concentration (color density), and sufficient brightness. . Moreover, when there are too many pigments, the compounding ratio of main components (A), (B), and (C) of a binder system will become comparatively small, and a film property will become inadequate easily.
[189] (solvent)
[190] In order to prepare the said inkjet ink composition for color filters of this invention with a high concentration liquid or the ink which can be immediately discharged from a head, (E) solvent is mix | blended as needed.
[191] The ink jet ink composition for color filters of the present invention has excellent discharge stability from the ink jet head because of excellent binder stability (viscosity stability), but has a boiling point of 180 ° C. in order to further improve discharge properties. A solvent component having a vapor pressure of 260 Pa, in particular 210 ° C. to 260 ° C. and a room pressure (especially in the range of 18 ° C. to 25 ° C.) of 133 Pa (0.5 mmHg) or less, especially 26.6 Pa (0.1 mmHg) or less, is used as the main solvent Such main solvent is preferably blended in an amount of 80% by weight or more, particularly preferably 85% by weight or more, based on the total amount of the solvent (E). Moreover, it is preferable that the surface tension of a main solvent is 29 dyn / cm or more.
[192] A solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure of 133 Pa (0.5 mmHg) or less at room temperature has suitable drying property and evaporation property. Therefore, when a single solvent or a mixed solvent containing such a solvent component at a high blending ratio is used, it does not dry rapidly at the tip of the nozzle of the recording head, so that a sudden increase in viscosity or clogging of the ink does not occur, and the straightness of ejection is achieved. It does not adversely affect stability. At the same time, after spraying on the surface to be discharged, drying proceeds at an appropriate speed, so that the ink fuses well with the surface to be coated so that the surface of the coating layer is horizontal and smooth, and then the ink is quickly and completely dried by natural drying or a general heating process. You can. Compared with the case of using a wetting agent or a solvent having a very high boiling point, there is less possibility that the solvent remains in the coating film after the drying step.
[193] When using a pigment as a coloring agent in the ink composition of this invention, a pigment is previously mixed with a dispersing agent in the some solvent of the total usage amount, and dispersibility is given, and the obtained pigment dispersion (that is, a pigment concentration liquid of high concentration) is mix | blended another In many cases, the component is added to the remaining solvent and mixed to form an ink composition. In order to prepare a pigment dispersion, it is necessary to use the solvent which is easy to disperse pigment, such as 3-methoxybutyl acetate and a propylene glycol monomethyl ether acetate (PGMEA).
[194] The solvent (E) of the ink composition may contain a small amount of solvent components other than the main solvent as necessary, such as a dispersion solvent used to prepare a pigment dispersion. However, even in that case, it is necessary to use the main solvent having the boiling point and the vapor pressure in a ratio of 80% by weight or more based on the total amount of the solvent. When the ratio of the main solvent does not account for 80% by weight of the total amount of the solvent, the drying property and the evaporability suitable for the ink jet method cannot be reliably obtained.
[195] The main solvent is preferably used in as high a blending ratio as possible. Specifically, the main solvent is preferably at least 80% by weight or more, preferably 85% by weight or more, and preferably 100% by weight. Therefore, it is preferable to mix and use a main solvent as a dispersion solvent, or to use it as it is at the time of preparation of a pigment dispersion, by selecting a main solvent suitably.
[196] By forming a wettability variable layer on the surface of the substrate and exposing it, a lip ink region is formed on a portion where an ink layer on the substrate is to be formed, and the ink composition of the present invention is selectively attached to the lip ink region by an ink jet method. In order to make the main solvent, the standard solution shown in the wettability test specified in JIS K6768 was used as the main solvent, the contact angle θ after 30 seconds was measured by contacting the droplets, and the critical surface tension determined by the graph of the Jigsman plot was 30 mN. the contact angle with respect to the surface of the test piece of / m is 25 degrees or more, preferably 30 degrees or more, and the contact angle with respect to the surface of the test piece whose critical surface tension calculated | required by the same measuring method is 70 mN / m shows less than lO degrees. You may select and use it.
[197] When the ink composition is prepared using a solvent exhibiting the above behavior with respect to the wettability, the ink composition exhibits large repulsion against the surface of the wettability variable layer before changing the wettability of the wettability variable layer described later. After changing the wettability of the layer to change in the direction of increasing hydrophilicity, it shows great affinity for the surface of the wettability variable layer. Accordingly, the difference between the wettability of the ink composition with respect to the ink repellent region formed by selectively exposing a part of the surface of the wettability variable layer and the wettability of the ink composition with respect to the ink repellent region around it can be made large. The ink composition sprayed on the ink region by the inkjet method is uniformly wetted and widened to every corner of the inking region. As a result, the pattern of the fine and stationary ink layer can be formed by the inkjet method.
[198] Here, the test piece having the above characteristics with respect to the critical surface tension may be formed of any material. As a test piece showing a critical surface tension of 30 mN / m, for example, the polymer, the surface modifier, or the like may be applied to a polymethyl methacrylate, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, or a smooth glass surface. Among the applied ones, one can actually select the corresponding one by performing the above test. Moreover, as a test piece which shows a critical surface tension of 70 mN / m, the said thing can be selected by actually performing the said test, for example among nylon, the glass which hydrophilized the surface, etc.
[199] The main solvent can be selected from among solvents as shown below: glycol ethers such as ethylene glycol monoethyl ether; Glycol ether esters such as ethylene glycol monomethyl ether acetate; Glycol oligomer ethers such as diethylene glycol monomethyl ether; Glycol oligomer ether esters such as diethylene glycol monomethyl ether acetate; Aliphatic carboxylic acids such as acetic acid, 2-ethylhexanoic acid and acetic anhydride or acid anhydrides thereof; Aliphatic or aromatic esters such as ethyl acetate and propyl benzoate; Dicarboxylic acid diesters such as diethyl carbonate; Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate; Ketocarboxylic acid esters such as ethyl acetoacetate; Halogenated carboxylic acids such as chloroacetic acid and dichloroacetic acid; Alcohols or phenols such as ethanol, isopropanol and phenol; Aliphatic or aromatic ethers such as diethyl ether and anisole; Alkoxy alcohols such as 2-ethoxyethanol and 1-methoxy-2-propanol; Glycol oligomers such as diethylene glycol and tripropylene glycol; Amino alcohols such as 2-diethylaminoethanol and triethanolamine; Alkoxyalcohol esters such as 2-ethoxyethyl acetate: ketones such as acetone and methyl isobutyl ketone; Morpholines such as N-ethyl morpholine and phenyl morpholine; Aliphatic or aromatic amines such as pentylamine, tripentylamine, aniline.
[200] Moreover, as a main solvent which occupies most of a solvent (E), especially a solvent, it is preferable to use the solvent which does not contain a hydroxyl group. If the solvent contains a hydroxyl group, in addition to the poor dispersibility and dispersion stability of the pigment, the dissociation of the blocking agent of the carboxyl group compound (B) is promoted, so that the carboxyl group is easily expressed, so that the epoxy compound (A) and It reacts with the epoxy group which a polyfunctional epoxy resin (C) has, and there exists a possibility of impairing storage stability (viscosity stability).
[201] Therefore, by using the solvent which does not contain a hydroxyl group as a solvent (E), the viscosity stability of an ink composition further improves and the ink excellent in ejection property and storage stability is obtained.
[202] Preferable examples of the main solvent include ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipic acid, dibutyl oxalate, dimethyl malonate, Diethyl malonate, dimethyl succinate, diethyl succinate, etc. can be illustrated. These solvents have a boiling point of 180 ° C to 260 ° C and a vapor pressure at room temperature of not more than 133 Pa (0.5 mmHg), and do not have a hydroxyl group in the molecule. Do not. In addition, these solvents may be used as a dispersing solvent without mixing or mixing with solvents conventionally used for preparing pigment dispersions such as 3-methoxyethyl acetate and propylene glycol monomethyl ether acetate (PGMIA). Dispersions can be prepared.
[203] The above-mentioned solvents exemplified as the preferred ones use the standard solution indicated in the wettability test specified in JIS K6768, and contact the droplets to measure the contact angle (θ) 30 seconds later, and the critical surface tension determined by the graph of the Jigsman plot is The contact angle with respect to the surface of the test piece of 30 mN / m shows 25 degrees or more, and the critical surface tension calculated | required by the same measuring method also satisfy | fills the request that the contact angle with respect to the surface of the test piece of 70 mN / m shows 10 degrees or less. . Therefore, these solvents can be suitably used as a main solvent even when the wettability variable layer is formed on the substrate surface and exposed, and the ink composition is selectively attached using the wettability difference between the exposed portion and the unexposed portion.
[204] In addition, even when water is mixed in the solvent, the hydroxyl groups of the water are present in the solvent, which may cause the same problem as in the case of using a solvent having a hydroxyl group. Therefore, in order to substantially exclude moisture from the crosslinking reaction system between acid and epoxy, it is preferable to prepare a coating liquid using a solvent having low miscibility with water. From such a viewpoint, it is preferable that the solubility with respect to the water of the solvent which prepares an ink composition is 20 weight part or less with respect to 100 weight part of water of 20 degreeC.
[205] In the main solvent mentioned as a specific example, diethylene glycol monobutyl ether acetate does not have a hydroxyl group, and since it exhibits solubility in 6.5 parts by weight and low water miscibility with 100 parts by weight of water having a liquid temperature of 20 ° C. , Especially preferred.
[206] The solvent (E) is usually used in the proportion of 40 to 95% by weight relative to the total amount of the ink composition containing the solvent to prepare the ink composition. If the solvent is too small, the viscosity of the ink is high, and the ejection from the ink jet head becomes difficult. In addition, when there are too many solvents, the ink filling amount (ink deposition amount) with respect to a predetermined wettability change site | part (ink layer formation site | part) is not enough, and the film | membrane of the ink deposited on this wettability change site | part collapses, and it becomes a non-exposure part to the surroundings. It comes out or spreads to the nearby wettability change site | part (ink layer formation site | part). In other words, the ink filling amount that can be deposited is not insufficient because it does not protrude from the wettability change site (ink layer forming site) to which the ink is to be deposited, so that the film thickness after drying is too thin, and thus has sufficient color density and luminance. Transmission light cannot be obtained.
[207] (Method for Producing Ink Composition)
[208] When the inkjet ink composition of this invention is not mix | blended with a pigment, it can normally manufacture by melt | dissolving and disperse | distributing each material including an epoxy compound (A) in arbitrary order suitably. However, if the liquid temperature of the solvent is too high, the protecting group of the carboxyl group block compound (B) is separated and the carboxyl group is regenerated in the step of preparing the ink composition. Thus, the liquid temperature of the solvent does not regenerate the carboxyl group of the carboxyl group block compound (B). Temperature is about 50 degrees C or less normally, Preferably it adjusts to the range of about 20-30 degreeC.
[209] In the present invention, the poorly soluble polybasic carboxylic acid is formed into a high soluble carboxyl group block compound (B) by blocking (capping and protecting) the carboxyl group of the polybasic carboxylic acid, and then dissolved and dispersed in a solvent. Therefore, the reaction point of the carboxyl group can coexist in the ink composition at high concentration, and when the ink layer is formed and heated using such ink composition, a high crosslinking density is obtained. Moreover, a carboxy group block compound (B) does not regenerate a carboxy group unless it heats more than the predetermined temperature which concerns on this compound. Therefore, despite the high reaction point concentration of each of the carboxyl group and the epoxy group, it is difficult to increase the viscosity during the discharge from the ink jet printing head, so that the straightness in the discharge direction from the ink jet printing head and the stability of the discharge amount are high. At the same time, in the state of the ink composition, a good viscosity is maintained for a long time immediately after preparation, and is also excellent in storage stability.
[210] Among the ink jet inks for color filters according to the present invention, preferred is the initial viscosity of 0.1 to 100 cps immediately after preparation, which is prepared and immediately placed in an airtight container and left at 20 ° C. for 40 days to determine the initial viscosity. It can be suppressed by thickening within 10%.
[211] When a pigment is directly thrown into the whole solvent with other components, such as a binder component, and it carries out stirring mixing, the pigment cannot be fully disperse | distributed in a solvent in many cases. Therefore, when mix | blending a pigment with the inkjet ink composition for color filters of this invention, the solvent which is excellent in the dispersibility and dispersion stability of a pigment is normally prepared, a pigment is added together with a dispersing agent, and it fully stirred by a solvent etc., A pigment dispersion is prepared. And the obtained pigment dispersion can be made into the ink composition which concerns on this invention by adding to the solvent which consists mostly of a main solvent, or consists only of a main solvent with components other than a pigment, and fully stirring and mixing with a solvent etc.
[212] As a solvent of the remainder to which a pigment dispersion is thrown in, the thing which has the composition which subtracted only the solvent used for preparation of a pigment dispersion from the composition of the final whole solvent may be used, and you may dilute to the final density and complete an ink composition. In addition, a pigment dispersion may be added to a relatively small amount of a main solvent to prepare a high concentration ink composition. The high concentration ink composition can be preserved as it is, diluted to the final concentration immediately before use, and used in the inkjet method.
[213] In the present invention, a solvent component (particularly a solvent component not containing a hydroxyl group) having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure of 133 Pa (0.5 mmHg) or less at room temperature is used in a proportion of 80% by weight or more of the whole solvent. It is preferable to use the containing sole solvent or mixed solvent. However, in order to make the final concentration of the main solvent 80% by weight or more of the entire solvent, conventionally used dispersion solvents such as 3-methoxybutyl acetate or propylene glycol monomethyl ether acetate (PGMEA) at the time of preparation of the pigment dispersion. You may not be able to use a sufficient amount of. In that case, among the solvents usable as the main solvent, those having a relatively good dispersibility and dispersion stability of the pigment are selected, and those mixed with a conventionally used dispersion solvent are used as the dispersion solvent, or such pigment dispersibility is relatively high. A good main solvent is used as a dispersing solvent as it is.
[214] (Production method of color filter)
[215] The ink jet ink composition for a color filter according to the present invention is selectively attached to a predetermined area on a transparent substrate of the color filter by an ink jet method to form an ink layer of a predetermined pattern, and then the ink layer is heated and cured. The cured resin layer as a detail of a color filter, such as a pixel part, a black matrix layer, a columnar spacer, a protective film, can be formed.
[216] (1) first method
[217] An example of the color filter manufacturing method using the ink for pixel part formation which mix | blended a pigment as an inkjet ink composition for color filters which concerns on this invention is demonstrated below. First, as shown in FIG. 4 (A), the transparent substrate 15 of the color filter is prepared. The transparent substrate is not particularly limited as long as it has been conventionally used for a color filter. For example, transparent rigid without flexible such as quartz glass, Pyrex glass (registered trademark), synthetic quartz plate, etc. Ash or a transparent flexible material having flexibility such as a transparent resin film and an optical resin plate can be used. Among these, 7059 glass made from Corning Corporation is a material with a small thermal expansion rate, is excellent in dimensional stability and workability in high temperature heat treatment, and is an alkali free glass containing no alkali component in the glass. It is suitable for the color filter for color liquid crystal display devices by. In the present invention, a transparent substrate is usually used, but even a reflective substrate or a substrate colored in white can be used. Moreover, you may use for the board | substrate what surface-treated for alkali elution prevention, gas barrier property provision, etc. as needed.
[218] Next, as shown in FIG. 4B, the black matrix layer 16 is formed in a region that becomes a boundary between the pixel portions of one surface side of the transparent substrate 15. The black matrix layer 16 can be formed by forming a metal thin film such as chromium having a thickness of about 1000 to 2000 Pa by a sputtering method, a vacuum vapor deposition method, or the like, and patterning the thin film. As this patterning method, a normal patterning method such as sputtering can be used.
[219] The black matrix layer 16 may be a layer containing light blocking particles such as carbon fine particles, metal oxides, inorganic pigments and organic pigments in the resin binder. As a resin binder used, 1 type (s) or 2 or more types of resins, such as a polyimide resin, an acrylic resin, an epoxy resin, polyacrylamide, polyvinyl alcohol, gelatin, casein, cellulose, a photosensitive resin, and O / W Emulsion type resin composition, for example, what emulsified reactive silicone, etc. can be used. As thickness of such a resin black matrix layer, it can set within the range of 0.5-10 micrometers. As a patterning method of such a resin black matrix layer, the method generally used, such as the photolithographic method and the printing method, can be used.
[220] Next, as shown in Fig. 4C, an ink repellent convex portion 17 having a width smaller than that of the black matrix layer is formed in the center of the pattern width direction of the black matrix layer as necessary. The composition of such an ink repellent convex part will not be specifically limited if it is a resin composition which has ink repellency. Moreover, it does not need to be especially transparent, It may be colored. For example, as a material used for a black matrix layer, the material etc. which do not mix black material can be used. Specifically, one or two or more kinds of aqueous resins such as polyacrylamide, polyvinyl alcohol, gelatin, casein and cellulose are mixed, or an O / W emulsion type resin composition, for example, reactive silicone And the like. In the present invention, a photocurable resin is suitably used for reasons such as ease of handling and curing. Moreover, since the ink repellent convex part is so preferable that ink repellency is strong, the surface may be processed with the ink repellent treatment agent, such as a silicone compound and a fluorine-containing compound.
[221] Patterning of the ink repellent convex portion can be performed by printing using a coating liquid of the ink repellent resin composition or photolithography using a photocurable coating liquid. Since the height of the ink repellent convex portion is formed so as to prevent the ink from being mixed when colored by the ink jet method as described above, it is preferable to be somewhat high, but considering the flatness of the whole when the color filter is used. In other words, the thickness is preferably close to the thickness of the pixel portion. Although it changes also with the deposition amount of the ink to spray specifically, it is preferable to exist in the range of 0.1-2.0 micrometers normally.
[222] Next, the ink composition for pixel part formation of various colors which concerns on this invention which the pigment of R, G, or B was mix | blended is prepared. And as shown in FIG.4 (D), it respond | corresponds to the pixel part formation area | region 18R, 18G, 18B of each color formed in the surface of the transparent substrate 15 by the pattern of the black matrix layer 16. FIG. An ink layer is formed by spraying the ink for forming the pixel portion of the color to be colored by an ink jet method. The ink layer is formed such that the red pattern, the green pattern, and the blue pattern are arranged in a desired form such as mosaic, stripe, triangle, quadrangular arrangement, and the like. In the ink spraying step, the pixel portion forming ink is less likely to cause an increase in viscosity at the tip end of the head 19, so that good ejectability can be maintained. Therefore, the ink of the corresponding color can be accurately and uniformly adhered in the predetermined pixel portion formation region, and a pixel portion free of color unevenness or color omission can be formed in an accurate pattern. In addition, since the ink for forming the pixel portion may be sprayed onto the substrate at the same time using a plurality of heads, the work efficiency can be improved as compared with the case where the pixel portion is formed for each color by a printing or the like method. In addition, since the stability of the ink composition according to the present invention is high as described above, the remaining liquid of the ink composition, which has been left in use once, has not been deteriorated yet in a short time operation. Therefore, such a balance can be recovered or reused by pouring and adding a fresh ink composition, which is economical.
[223] Next, as shown in Fig. 4E, the various ink layers 20R, 20G, and 20B are solidified by drying and then cured by heating. When the ink layer is heated, the protecting group of the carboxyl group compound (B) described above contained in the ink layer is separated, and the carboxyl group is regenerated from the functional group represented by the formula (1), and the epoxy compound (A) and the polyfunctional epoxy resin (C) The branch causes a crosslinking reaction with the epoxy group, and the ink layer is cured. The thickness of the pixel portion is usually about 0.1 to 2.0 mu m in consideration of optical characteristics and the like.
[224] In this drying and thermosetting step, after drying and solidifying the coating film by prebaking heating, the temperature is generally higher than that during prebaking to perform postbaking heating to perform thermal curing, but the heating temperature of the prebaking is relatively high. When it is high or when the dissociation temperature of a blocked carboxyl compound (B) is comparatively low, the thermosetting reaction may be started in part at the stage of prebaking.
[225] In the present invention, the prebaking is preferably performed at a high temperature as much as possible, as long as it is not disclosed or difficult to proceed even if partially disclosed as long as it can be a thermosetting reaction. This is because by performing the prebaking at a high temperature, such a time is shortened in the drying step to improve productivity, and a cured film having a high flatness can be obtained even when there is irregularities in the cured film or base having a uniform film thickness.
[226] That is, when the ink composition according to the present invention is sprayed onto the surface to be coated by the ink jet method, the central portion as shown in Fig. 6 becomes a convex coating film by surface tension, and when it is dried, it solidifies as it is, and then the thermal curing. Also, the cured film 27a is formed with convex shape maintained. In this way, when curing while maintaining the convex shape at the time of spraying, in the case of forming a colored film such as a pixel, the film thickness becomes uneven, and the color density and luminance at the end are insufficient, resulting in color unevenness (color difference between the end and the center part ( In the case of forming a relatively large-area coating film such as a protective film, it is an obstacle to absorbing the unevenness of the base and flattening the surface.
[227] On the other hand, when this convex coating film is dried at high temperature in the state of still high fluidity | liquidity in a prebaking stage, the evaporation rate of a solvent, ie, a drying rate, becomes very large compared with the center part with a thick film thickness at the thin film edge part. . A large concentration gradient is formed by the accelerated drying at this end, which increases the amount of solvent moving to the end, thereby increasing the amount of solute moving, and consequently, the film thickness of the end is increased. Therefore, by performing the prebaking at such a high temperature, it is possible to make the film thickness of the coating film uniform or to make the surface of the coating film flat, and the film thickness as shown in FIG. A cured film with uniform or high flatness is obtained.
[228] However, when the heating temperature at the time of prebaking is too high, the problem that a crack occurs easily in a coating film arises newly. That is, when prebaking is performed at a high temperature, the drying is too fast, so the film reduction (volume reduction of the coating film) proceeds rapidly and cracks are likely to occur. In particular, when a coating film is formed by using an ink composition containing a carboxyl group compound (B) having a low dissociation temperature of vinyl ether, and a high temperature prebaking is performed, the film reduction (reduction of the volume of the coating film) proceeds rapidly. In parallel with this, since the dissociation temperature of the vinyl ether is reached in this prebaking step, and the thermosetting reaction of the epoxy compound also proceeds, the distortion inside the coating film becomes large and cracks are more likely to occur.
[229] This problem of cracking can be prevented by using a carboxyl group compound (B), more preferably both of which is a main polymer (A ') or primary alkyl vinyl ether having a Tg of 70 ° C. or lower, as described above. Even if the coating film is dried at a high temperature during the prebaking, it is estimated that the flexibility capable of absorbing the distortion generated inside the coating film during prebaking can be maintained.
[230] According to the experiments of the present inventors, when the coating film is heated to about 80 ° C. and dried at the time of prebaking, no crack is generated, but a convex cured film 27a as shown in FIG. 6 is obtained. For example, when a cured film is a pixel, the color density of the edge part was thin and the color difference with the center part became large. Moreover, when the coating film was heated at about 100 degreeC or more at the time of prebaking, a crack was easy to generate | occur | produce.
[231] On the other hand, the Tg as mentioned above is a carboxyl group compound (B) by the main polymer (A ') of 70 degrees C or less, or primary alkyl vinyl ether, More preferably, the ink composition which mix | blended both was carried out to the to-be-coated surface. In the case of spraying by the inkjet method, cracks did not occur even when the coating film was heated to dry at about 100 ° C or more during prebaking. In addition, the cured film 27b finally obtained as shown in FIG. 7 has high flatness, for example, when a cured film is a pixel, it is the position of 3/4 of the width n from the center P1 to the edge part. The color difference DELTA Eab of (P2) can be 6 or less, preferably 3 or less, and color unevenness cannot be recognized by the naked eye.
[232] In order to improve the flatness of a coating film further, it was effective to make heating temperature (coating film temperature) at the time of prebaking into about 120 degreeC or more, especially 140 degreeC or more. Moreover, heating under reduced pressure was also effective for improving flatness and shortening the drying time. However, when the heating temperature at the time of prebaking exceeds about 160 degreeC, an undried coating film will become easy to produce a dolby.
[233] From the results of these experiments, in the present invention, in order to obtain a coating film having a uniform film thickness or a flat surface, the coating film of the ink composition is 100 ° C or more, particularly 120 ° C or more, more preferably 140 ° C or more, and further, a carboxyl group block. It is preferable to carry out prebaking by heating to the temperature of 160 degrees C or less range which is the temperature which the block part of a compound does not dissociate, and Dolby does not arise, and it was turned out that drying under reduced pressure at that time is more preferable. And after prebaking, heating temperature is raised beyond the dissociation temperature of a carboxyl group compound, for example, 200 degreeC, and post-bakes for about 1 hour, and the cured film with high flatness is obtained.
[234] And when performing such high temperature prebaking and postbaking, Tg is 70 degreeC or less main polymer (A ') or the carboxy group block compound (B) by primary alkyl vinyl ether, More preferably, both of these are Since the occurrence of cracks can be prevented by using an ink composition containing, a cured film having high flatness and no cracks is obtained.
[235] Next, as shown in FIG. 4F, the protective film 22 is formed on the side where the pixel portions 21R, 21G, 21B of the transparent substrate are formed. The thickness of a protective film can be set in consideration of the light transmittance of the material used, the surface state of a color filter, etc., for example, can be set in the range of 0.1-2.0 micrometers. For the protective film, for example, a coating liquid for a protective film is prepared using a known transparent photosensitive resin, a two-liquid curable transparent resin, or the like having a light transmittance required as a transparent protective film, and a spin coater for 500 to 1500 revolutions / minute. It can form by apply | coating within the range of.
[236] The transparent electrode on the protective film is formed by a general method such as sputtering method, vacuum deposition method, CVD method using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), or an alloy thereof, and the like. If necessary, it is made into a predetermined pattern by etching using a photoresist or use of a jig. The thickness of this transparent electrode can be about 20-500 nm, Preferably it is about 100-300 nm.
[237] When forming a columnar spacer on a transparent electrode, the coating liquid of a photocurable resin composition is apply | coated by methods, such as a spin coater, a roll coater, a spray, and printing, and it exposes by ultraviolet irradiation through a photomask, and alkali After image development, it can form by heat-hardening by a clean oven etc. The columnar spacer is formed at a height of, for example, about 5 μm. The number of revolutions of the spin coater may be set within the range of 500 to 1500 revolutions per minute, as in the case of forming a protective film.
[238] In this way, the color filter 103 is manufactured using the inkjet ink composition for color filters which concerns on this invention. And a liquid crystal panel is obtained by forming an oriented film in the inner surface side of this color filter, opposing an electrode substrate, and sealing a liquid crystal in a gap part.
[239] In this example, the pixel portion is formed using the ink composition of the present invention. According to the ink jet method using the ink jet ink for color filters according to the present invention, a black matrix layer, a columnar spacer, a protective film, and the like can be formed in a desired pattern shape in addition to the pixel portion, but high definition as in the pixel portion and the black matrix layer. The use value is especially high in the point which can form the colored layer to which a drawing is calculated | required.
[240] (2) second method
[241] The wettability in a predetermined region of the substrate surface of the color filter is selectively changed to form an ink layer forming region having a larger ink ink relative to the surroundings, and the ink composition according to the present invention is applied to the ink layer forming region. By selectively adhering to form an ink layer and hardening the ink layer, in particular, a cured resin layer having a fine pattern can be accurately formed.
[242] For example, on a transparent substrate of a color filter, a wettability variable layer is formed on the transparent substrate of the color filter which changes wettability in a direction in which the ink ink becomes large, and the wettability in a predetermined region of the wettability variable layer surface is selectively selected by exposure. To form an ink layer forming region having a larger ink ink relative to the surroundings, and selectively attaching the ink composition according to the present invention to the ink layer forming region by an inkjet method to form an ink layer. It is possible.
[243] When forming such a wettability variable layer on a board | substrate, as a main solvent, the standard liquid shown by the wettability test prescribed | regulated to JISK6768 was used, the contact angle ((theta)) after 30 second was made to contact a droplet, and the Jisman plot was carried out. The contact angle with respect to the surface of the test piece whose critical surface tension calculated | required by the graph of 30 mN / m is 25 degrees or more, and the contact angle with respect to the surface of the test piece whose critical surface tension is 70 mN / m calculated | required by the same measuring method is 10 degrees. It is preferable to use the ink composition prepared using what is shown below.
[244] An example of the 2nd manufacturing method of such a color filter is demonstrated below. First, as shown in FIG. 5 (A), the black matrix layer 16 is formed in the area | region which becomes a boundary between the 1-side side pixel part of the transparent substrate 15 of a color filter. According to the pattern of the black matrix layer, various pixel portion formation regions 18R, 18G, and 18B are partitioned. As the transparent substrate 15, the same ones used in the first method described above can be used, and the black matrix layer 16 can also be formed in the same manner as in the first method.
[245] Next, as shown in FIG. 5B, the photocatalyst-containing layer 23 as the wettability variable layer is formed in at least a portion of the surface of the transparent substrate 15, particularly in this example, the region including the pixel portion formation region. To form a pattern without a picture (solid pattern).
[246] Next, as shown in FIG. 5C, the photocatalyst-containing layer 23 is irradiated with light rays 26 through a photomask 24 to perform exposure, and the pixel portion formation regions 18R, 18G, and 18B are exposed. Increase the ink ink of the.
[247] When the wettability of the pixel portion formation region of the wettability variable layer such as the photocatalyst-containing layer 23 is selectively changed to increase the ink repellency, the ink composition of the present invention is easily attached to the pixel portion formation region and is uniformly widened. On the other hand, in the peripheral region of the pixel portion formation region, it is strongly repelled and excluded, so that it is selectively and uniformly attached to the pixel portion formation region, and as a result, a pixel portion without color unevenness or color omission in an accurate pattern can be formed.
[248] As the wettability variable layer used in the second method, the critical surface obtained by using the standard solution presented in the wettability test specified in JIS K6768, measuring the contact angle (θ) after 30 seconds by contacting the droplets, and obtaining the graph by the graph of the Jisman plot It is preferable that tension shows 20-50 mN / m before changing wettability, and 40-80 mN / m after changing wettability.
[249] When the wettability variable layer capable of changing the critical surface tension in this way is used, the ink composition exhibits a very small contact angle in a pattern formation region such as a pixel portion formation region where the wettability is changed to increase the ink inks, while the pattern In the circumference | surroundings of a formation area, a very large contact angle is shown and the difference of wettability can be taken very much.
[250] In the case of performing exposure using the photomask 24, the width of the exposure portion 25 is made wider than the width of the pixel portion formation region 18 while securing the unexposed portion at the boundary between adjacent pixel portion formation regions. It is desirable to hold. By doing in this way, since every corner of the pixel part formation area | region 18 is fully exposed, and an ink repellency increases, the problem of the color part of a pixel part etc. does not arise. The photocatalyst-containing layer 23 may be exposed in a predetermined pattern by another method such as photolithography by scanning a laser beam without using a photomask. In addition, when exposure is performed from the back side of the transparent substrate (the side opposite to that on which the photocatalyst-containing layer 23 is formed), the black matrix layer 16 functions as a photomask, so that a photomask is unnecessary.
[251] Although the light irradiated to the photocatalyst-containing layer 23 can be a visible light or an invisible light as long as it can activate a photocatalyst, the light containing ultraviolet light is normally used. As a light source containing such ultraviolet light, a mercury lamp, a metal halide lamp, a xenon lamp, etc. are mentioned, for example. The wavelength of the light used for this exposure can be set within the range of 400 nm or less, preferably 380 nm or less, and the irradiation amount of light in the exposure is an irradiation amount necessary for the exposed portion to increase hydrophilicity by the action of the photocatalyst. can do.
[252] As the wettability variable layer capable of changing the wettability in the direction of increasing the ink-inking property, for example, a) the hydrophilicity of the wettability variable layer itself is contained by the action of the photocatalyst as shown in the photocatalyst-containing layer 23 shown. In addition to the increase, b) a photocatalyst-containing layer below the wettability variable layer (transparent substrate side), and the hydrophilicity of the wettability variable layer is increased by the action of the photocatalyst present in the photocatalyst-containing layer, c) the photocatalyst and the photocatalyst A decomposable wettability variable layer comprising a binder decomposed by the action of, wherein the exposed portion of the decomposable wettability variable layer is decomposed and removed to expose a base having a hydrophilic property, such as a transparent substrate, or d) of a photocatalyst. A photocatalyst-containing layer is provided below the decomposable wettability variable layer made of a binder decomposed by the action, and is contained in the photocatalyst-containing layer. By the action of the photocatalyst present having a hydrophilic is the exposed portion of the wettability-variable layer decomposable decomposition, removal and the like can be given will be based, for example, such photocatalyst-containing layer is exposed.
[253] In the present invention, the "wetting variable layer capable of changing the wettability in the direction in which the ink ink becomes large" is a laminate formed by forming a wettability variable layer on a substrate. It is only necessary to change the direction in a larger direction, and as shown in the examples a) and b), not only the affinity of the wettability variable layer itself is increased, but also as in the examples c) and d), the wettability variable layer is decomposed and the inking is performed. This includes exposing the sex base.
[254] Hereinafter, the types of a) and b) will be described in detail.
[255] a) photocatalyst containing layer which increases its hydrophilicity
[256] Like the photocatalyst-containing layer 23 shown, the photocatalyst-containing layer, which itself functions as a wettability variable layer, is dispersed in a solvent with other additives as needed to prepare a coating liquid, and after applying the coating liquid. And hydrolysis and polycondensation reaction to advance and fix a photocatalyst firmly in a binder.
[257] As the photocatalyst, for example, titanium oxide (TiO ₂ ), zinc oxide (ZDO), tin oxide (SnO ₂ ), strontium titanate (SrTiO ₃ ), tungsten oxide (WO ₃ ), bismuth oxide (Bi) ₂ O _3), and iron oxide (may be mentioned Fe ₂ O _3), it may be used by mixing one or more kinds selected from them.
[258] The mechanism of action of the photocatalyst in the photocatalyst-containing layer is not necessarily clear, but the carrier produced by irradiation of light changes in the chemical structure of the organic material by the direct reaction with the compound nearby or by the active oxygen species generated in the presence of oxygen or water. It is thought that the hydrophilicity is increased by, for example, oxidation, decomposition, or the like of an organic group or an additive which is a part of the binder.
[259] In the present invention, titanium oxide is particularly suitably used because of its high band gap energy, chemical stability, no toxicity, and easy availability. Titanium oxide has an anatase type and a rutile type, and both can be used in the present invention, but an anatase type titanium oxide is preferable. The anatase titanium oxide has an excitation wavelength of 38 Onm or less.
[260] As such anatase type titanium oxide, for example, anatase-type titania sol of hydrochloric acid bridge type (STS-02 (Ishihara Sangyo Co., Ltd.) STS-02 (average particle diameter 7nm), Ishihara Sangyo Co., Ltd. ST-K01) And anatase-type titania sol (TA-15 (average particle diameter 12 nm) manufactured by Nissan Gaku Co., Ltd.) of nitric acid bridge type.
[261] The smaller the particle size of the photocatalyst is, the more effectively the photocatalytic reaction takes place. A photocatalyst having an average particle diameter of 50 nm or less is preferable, and a photocatalyst of 20 nm or less is particularly preferable. The smaller the particle size of the photocatalyst is, the smaller the surface roughness of the formed photocatalyst-containing layer is, and the lower the particle size of the photocatalyst is. It is unpreferable because this lowers and the expression of the lip ink of the exposed portion is insufficient.
[262] The binder used for this type of photocatalyst-containing layer preferably has a high binding energy in which the main skeleton is not decomposed by the photoexcitation of the photocatalyst, for example, (1) chloro or alkoxysilane or the like by a sol-gel reaction or the like. The organopolysiloxane which hydrolyzes, polycondenses, and exhibits great strength, (2) organopolysiloxane which bridge | crosslinked the reactive silicone excellent in water repellency and oil repellency, etc. are mentioned.
[263] In the case of (1), the following general formula (12):
[264] Y _n SiX _(4-n)
[265] (Wherein, Y represents hydrogen or a hydrocarbon group which may have a substituent. A plurality of Y in one molecule may be the same group or different groups. N is an integer of 0 to 3.)
[266] It is preferable that it is organopolysiloxane which is 1 type, or 2 or more types of hydrolysis condensation product or cohydrolysis condensation product of the silicon compound represented by.
[267] It is preferable that the silicon compound represented by the said General formula (12) has at least 1 hydrocarbon group which may have a substituent as Y.
[268] In the formula (12), as the unsubstituted hydrocarbon group or the hydrocarbon group portion of the substituted hydrocarbon group, for example, a straight or branched aliphatic hydrocarbon group such as methyl, ethyl or other alkyl; Alicyclic hydrocarbon groups such as cyclohexyl; Unsaturated hydrocarbon groups such as vinyl; Aromatic hydrocarbon groups, such as phenyl, etc. can be illustrated, It is preferable that carbon number of these hydrocarbon group or a hydrocarbon group part exists in the range of 1-20.
[269] Moreover, as a hydrocarbon group which may have a substituent in the said General formula (12), Fluorine-containing hydrocarbon groups, such as fluoroalkyl; Epoxy-containing hydrocarbon groups such as glycidoxyalkyl or β- (3,4-epoxycyclohexyl) alkyl; Acryloyloxy or methacryloyloxy-containing hydrocarbon groups such as (meth) acryloyloxyalkyl; Amino-containing hydrocarbon groups such as aminoalkyl; Mercapto-containing hydrocarbon groups such as mercaptoalkyl; Fluoroalkyl containing hydrocarbon groups, such as N-fluoroalkylsulfonamide group containing hydrocarbon groups, such as N-fluoroalkylsulfonylaminoalkyl, etc. can be illustrated.
[270] Moreover, it is preferable that the alkoxy group represented by X is a methoxy group, an ethoxy group, a propoxy group, butoxy group.
[271] Specifically, methyltrichlorosilane, methyltribromosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-t-butoxysilane; Ethyltrichlorosilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane; n-propyltrichlorosilane, n-propyltribromosilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane; n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane; n-decyltrichlorosilane, n-decyltribromosilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane; n-octadecyltrichlorosilane, n-octadecyltribromosilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltriisopropoxysilane, n-octadecyltri- t-butoxysilane; Phenyltrichlorosilane, phenyltribromosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriisopropoxysilane, phenyltri-t-butoxysilane; Tetrachlorosilane, tetrabromosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane; Dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane; Diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane; Phenylmethyldichlorosilane, phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane; Trichlorohydrosilane, tribromohydrosilane, trimethoxyhydrosilane, triethoxyhydrosilane, triisopropoxyhydrosilane, tri-t-butoxyhydrosilane; Vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane; Trifluoropropyltrichlorosilane, trifluoropropyltribromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t Butoxysilane; γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylethoxysilane, γ-glycidoxypropyltri Isopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane; γ-methacryloyloxypropylmethyldimethoxysilane, γ-methacryloyloxypropylmethyldiethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxy Silane, γ-methacryloyloxypropyl triisopropoxy silane, γ-methacryloyloxypropyl tri-t-butoxy silane; γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyl Tri-t-butoxysilane; γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltriisopropoxysilane γ-mercaptopropyltri-t-butoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; And their partial hydrolysates; And mixtures thereof.
[272] Moreover, as an organopolysiloxane compound, it is especially preferable to have a fluoroalkyl group. When the wettability variable layer is formed using an organopolysiloxane compound having a fluoroalkyl group, the water-repellent property and ink repellency of the non-exposed part are increased by the action of the fluoroalkyl group, and between the highly hydrophilized exposed part and the high water-repellent non-exposed part The difference in the wettability with respect to the ink can be made large.
[273] Specifically, as a hydrolysis condensate using the silicon compound represented by the general formula Y _n SiX _(4-n) as a condensation unit, or a cohydrolytic condensate, all or at least part of the condensation unit is One or two or more kinds of fluoroalkyl group-containing silicon compounds such as fluoroalkylsilanes can be used. The following fluoroalkylsilanes are generally known as fluorine silane coupling agents.
[274] CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
[275] CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
[276] CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
[277] CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
[278] (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
[279] (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
[280] (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ;
[281] CF 3 (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃ ;
[282] CF ₃ (CF ₂ ) ₃ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃ ;
[283] CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃ ;
[284] CF ₃ (CF ₂ ) ₇ (C ₆ H ₄ ) C ₂ H ₄ Si (OCH ₃ ) ₃ ;
[285] CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
[286] CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
[287] CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
[288] CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
[289] (CF ₃ ) ₂ CF (CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
[290] (CF ₃ ) ₂ CF (CF ₂ ) ₆ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
[291] (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ SiCH ₃ (OCH ₃ ) ₂ ;
[292] CF ₃ (C ₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ;
[293] CF ₃ (CF ₂ ) ₃ (C ₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ;
[294] CF ₃ (CF ₂ ) ₅ (C ₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ;
[295] CF ₃ (CF ₂ ) ₇ (C ₆ H ₄ ) C ₂ H ₄ SiCH ₃ (OCH ₃ ) ₂ ;
[296] CF ₃ (CF ₂ ) ₃ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ;
[297] CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ;
[298] CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ;
[299] CF ₃ (CF ₂ ) ₉ CH ₂ CH ₂ Si (OCH ₂ CH ₃ ) ₃ ; And
[300] CF ₃ (CF ₂ ) ₇ SO ₂ N (C ₂ H ₅ ) C ₂ H ₄ CH ₂ Si (OCH ₃ ) ₃ ;
[301] By using the above-mentioned polysiloxane containing a fluoroalkyl group as a binder, since the ink repellency before changing the wettability of a photocatalyst containing layer becomes large, the difference in wettability can be made large before and after changing wettability.
[302] Moreover, as reactive silicone of said (2), the compound which has frame | skeleton represented by following General formula (13) is mentioned.
[303] [Formula 13]
[304]
[305] Provided that n is an integer greater than or equal to 2, and R ¹ and R ² each represent a substituted or unsubstituted alkyl, alkenyl, allyl or cyanoalkyl group having 1 to 10 carbon atoms, with 40% or less of the total being vinyl, phenyl or halogenated in a molar ratio. Phenyl. Moreover, since the surface energy becomes the smallest, it is preferable that R <^1> , R <^2> is a methyl group, and it is preferable that a methyl group is 60% or more by molar ratio. In addition, at the terminal or side chain of a bran, it has reactive groups, such as at least 1 or more hydroxyl group, in a molecular chain.
[306] Moreover, you may mix with the said organopolysiloxane the stable organosilicon compound which does not perform crosslinking reaction like dimethylpolysiloxane to a binder.
[307] The photocatalyst-containing layer may contain a surfactant in addition to the photocatalyst and the binder. Specifically, hydrocarbon series, such as each series of Nikko Chemicals Corporation brand name NlKKO1 BL, BC, BO, BB, the brand name ZONYL FSN, FSO made by Dupont, brand name Saffron S-141 by Asahi Glass Co., Ltd. , 145, Dainippon ink Kagaku Kogyo Co., Ltd. brand name Mega akuku F-141, 144, Neos Co., Ltd. brand name Futagent F-200, F251, Daikin Kogyo Co., Ltd. brand name Uindain DS-401,402, Fluorine or silicone type nonionic surfactants, such as the 3M brand name Florade FC-l70, 176, etc. are mentioned, A cationic surfactant, anionic surfactant, and an amphoteric surfactant can also be used.
[308] In addition to the above surfactants, the photocatalyst-containing layer also contains polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, and polychlorinated salt. Vinyl, polyamide, polyimide, styrenebutadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide And oligomers such as polyisoprene, polymers and the like.
[309] Content of the photocatalyst in a photocatalyst containing layer can be set in 5 to 60 weight%, Preferably it is 20 to 40 weight%. Moreover, the thickness of a photocatalyst containing layer is preferable in the range of 0.05-10 micrometers.
[310] As a solvent which melt | dissolves and disperse | distributes said each component, alcohol-type organic solvents, such as ethanol and isopropanol, are preferable. Application can be carried out by known coating methods such as spin coating, spray coating, dip coating, roll coating, bead coating and the like. When the ultraviolet curable component is contained as the binder, the photocatalyst-containing layer can be formed by irradiating ultraviolet rays and performing a curing treatment.
[311] b) A photocatalyst-containing layer is provided below the wettability variable layer to increase the hydrophilicity of the wettability variable layer.
[312] To form this type of wettability variable layer, first, a coating liquid obtained by dissolving and dispersing a binder and a photocatalyst is applied onto a transparent substrate of a color filter, and then subjected to hydrolysis and polycondensation reaction to form a photocatalyst-containing layer. Alternatively, the photocatalyst-containing layer of the photocatalyst alone is formed. Next, the wettability variable layer of the thin film which consists of hydrophobic organic substance is formed on a photocatalyst containing layer. As a photocatalyst, a binder, a solvent, etc., you may use the thing similar to what is used by the type of said a).
[313] For forming a thin film of an organic substance, a film formation method by gas phase such as solution coating, surface graft treatment, surfactant treatment, PVD, CVD, or the like can be used. As an organic substance, it is a low molecular compound, a high molecular compound, surfactant, etc., and the thing which changes wettability by a photocatalyst can be used. Specifically, examples of the silane compound in which the organic group is changed to a hydroxyl group by the action of a photocatalyst include a silane coupling agent, chlorosilane, alkoxysilane, two or more kinds of hydrolysis condensates, and cohydrolysis condensates. On the photocatalyst containing layer, you may form the wettability variable layer which consists of organopolysiloxane mentioned above, In that case, it is preferable to use the organopolysiloxane containing a fluoroalkyl group.
[314] The wettable variable layer exemplified above is a photocatalyst-containing layer in which the wettable variable layer itself contains a photocatalyst, or is provided with a photocatalyst-containing layer formed on the transparent substrate side of the wettable variable layer, and the photocatalyst-containing layer is irradiated with light. By activating the photocatalyst, the action of the activated photocatalyst changes the wettability in the direction in which the parent ink is increased. That is, the wettability variable layers exemplify all change wettability in a direction in which the inking property becomes large as light rays are irradiated.
[315] However, in the present invention, the wettability variable layer is not particularly limited as long as the wettability variable layer is a layer which can change the wettability of the surface by a stimulus from outside, for example, a physical stimulus, a chemical stimulus, or the like. For example, it may be a layer in which the state of the surface roughness is changed due to an acid or an alkali, and the wettability is changed, or the substance in the wettability variable layer is changed by irradiation of energy such as ultraviolet rays, visible light, heat, or the like. The layer to be changed may be used.
[316] In addition, the photocatalyst-containing layer used in the above-described method increases the affinity of ink by irradiating the pixel portion forming region with light rays, and selectively attaches the ink composition, but has a wettability variable layer whose affinity of ink is reduced by any stimulus. It is possible to selectively attach the ink composition only to a desired region by forming it on the transparent substrate of the color filter and giving a stimulus for changing the wettability to the negative pattern of the pixel portion formation region.
[317] Next, as the ink jet ink composition for color filters according to the present invention, ink for forming pixel portions of various colors, which is formed by blending one or two or more pigments, is prepared. Then, the pixel portion forming ink of the corresponding color is selectively attached to the pixel portion forming regions 18R, 18C, and 18B in which the affinity ink is increased in the above-described process of FIG. 5C by an ink jet method. And ink layers 20R, 20G, and 20B as shown in Fig. 5D.
[318] Next, as shown in Fig. 5E, the various ink layers 20R, 20C, and 20B are solidified by drying, and then hardened by heating to form various pixel portions 21R, 21G, and 21B. do. Next, as shown in FIG. 5F, the protective film 22 is formed on the side where the pixel portions 21R, 21G, 21B of the transparent substrate are formed. In addition, the color filter 104 is manufactured by forming a transparent electrode and a columnar spacer on the protective film 22. The hardening process, the protective film formation process, the transparent electrode formation process, and the columnar spacer formation process in a 2nd method can be performed as with the 1st method.
[319] In this example, the pixel portion is formed using the pixel portion forming ink, which is the ink jet ink for color filters according to the present invention, but the ink composition according to the present invention is selectively selected only in the inking region using the difference in wettability of the substrate surface. By attaching it, the cured resin layer other than the pixel portion, such as a black matrix layer, a protective film, and a columnar spacer, can also be formed in a desired pattern shape.
[320] (Physical Properties of Cured Resin Layer)
[321] The cured resin layer formed by using the ink jet ink for color filters according to the present invention is excellent in transparency, hardness, heat resistance (degree of film reduction or discoloration due to heating), and various other properties required for color filter details. Do. For example, the cured resin layer which has the following hardness, heat resistance, etc. can be formed on a transparent substrate using the inkjet ink for color filters which concerns on this invention.
[322] a) Hardness: It shows the pencil hardness of 2H or more in the 8.4 * 1 test method in the pencil scraping test prescribed | regulated to JISK5400 (l990).
[323] b) Heat resistance: The film thickness reduction of the cured resin layer after leaving a color filter at 250 degreeC for 1 hour is 10% or less, and the color difference before and behind the said leaving can be 1 or less.
[324] c) Solvent resistance (chemical resistance): Cured after immersing the color filter in which the cured resin layer was formed in a solvent of any one of isopropyl alcohol, N-methylpyrrolidone or γ-butyrolactone at a solution temperature of 40 ° C. for 1 hour. The film thickness reduction calculated by measuring the film thickness of the resin layer can be 10% or less even when immersed in any solvent.
[325] d) Temperature-pure water resistance: After immersing the color filter in which the cured resin layer was formed in pure water of 80 degreeC for 1 hour, the result of having performed the board | substrate tape peeling test prescribed | regulated to JISK5400 (1990) 8.5 is six points. This can be done.
[326] It is guessed that the thing which the crosslinking density of the cured resin layer is very high contributes that the cured resin layer produced by this invention shows the outstanding hardness, solvent resistance, and temperature-temperature purity.
[327] EXAMPLE
[328] Production Example A Synthesis of Polymer (A)
[329] In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 40.7 solvents of diethylene glycol monobutyl ether acetate (alias butyl carbitol acetate, BCA) containing no hydroxyl group were added according to the blending ratio shown in Table 1. By weight, the mixture was heated while stirring, and the temperature was raised to 140 ° C. Subsequently, 54.7 parts by weight of a mixture (dripping component) of the monomer of the composition shown in Table 1 and the polymerization initiator at a temperature of 140 ° C. was added dropwise at a constant velocity through a dropping funnel over 2 hours. After completion of the dropping, the temperature was lowered to 110 ° C., and 4.6 parts by weight of a mixture (additional catalyst component) of a solvent diethylene glycol monobutyl ether acetate (BCA) containing no polymerization initiator and a hydroxyl group was added, and the temperature at 110 ° C. was maintained for 2 hours. By terminating reaction when hold | maintained, the main polymer (A'-1) and (A'-2) which have the characteristic of Table 1 were obtained.
[330] TABLE 1
[331]
[332] * 1) The symbol in a table | surface is as follows.
[333] GMA: glycidyl methacrylate
[334] MMA: Methyl methacrylate
[335] MEA: methoxyethyl acrylate
[336] Perbutyl O: t-butyl peroxy 2-ethylhexanoate (made by Nippon Shokai)
[337] 2) A'-1: MMA was used. A'-2: MEA was used.
[338] * 3) Appearance: Appears visually.
[339] * 4) Heating residue: The test was done by JIS-K5407 and 4. heating residue.
[340] * 5) Epoxy equivalent: After performing ring-opening reaction of epoxy group with excess 0.2N hydrochloric acid dioxane solution, unreacted hydrochloric acid was reverse titrated with 0.1NKOH ethanol solution, The epoxy equivalent was calculated.
[341] * 6) It measured with the E-type viscosity meter.
[342] * 7) Weight average molecular weight: Value of polystyrene conversion by gel permeation chromatography.
[343] Preparation Example B Synthesis of Blocked Carboxylic Acid Compound (B)
[344] Into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, a solvent, a raw material (polybasic carboxylic acid), and a blocking agent (vinyl ether) were added and stirred under heating according to the mixing ratio shown in Table 2). The temperature was raised to ° C. Then, stirring was continued, maintaining the temperature of 70 degreeC, reaction was complete | finished when the acid value of the mixture became 5 or less, and the blocked carboxylic acid compound (B-1) which has the characteristic of Table 2 was obtained.
[345] TABLE 2
[346]
[347] * 1) Acid value of the solution: Titrated with 0.1NKOH ethanol solution, and calculated.
[348] * 2) Block rate: From the acid value of the solution, it computed by converting solid content.
[349] * 3) Block acid solid content: Measured by gas chromatography (GC).
[350] * 4) Acid equivalent of solution: The acid value was measured after dissociating a block agent with the water methanol solution.
[351] * 5) Weight average molecular weight: Value of polystyrene conversion by gel permeation chromatography.
[352] (Examples 1 to 5)
[353] (1) Preparation of Binder
[354] A rotor coated with Teflon (registered trademark) was placed in a sample bottle, and a magnetic stirrer was installed. In this sample bottle, according to the mixing | blending ratio shown in Table 3, the main polymer (A ') of the said manufacture example A or (A'-2), the blocked carboxylic acid (B) of the said manufacture example B, and polyfunctional epoxy resin After adding (C) and a halogen free acidic catalyst (D '), and fully stirring and melt | dissolving, and then adding a diluting solvent and stirring-dissolving for viscosity adjustment, this is filtered and binder composition (alpha) -1-(alpha) -5 ( Solid content 40% by weight).
[355] TABLE 3
[356]
[357] * 1) The symbol in a table | surface is as follows.
[358] Ep # 828: bifunctional epoxy resin (brand name epi coat 828EL, product made in Japan epochish resin)
[359] Er # 157: four action epoxy resin (brand name epi coat 157S70, product made in Japan Epochshi resin)
[360] LC-1: Brand name Nofcure LC-1 (made by Nippon Yushisha)
[361] BCA: diethylene glycol monobutyl ether acetate
[362] * 2) It measured with the E-type viscosity meter.
[363] * 3) It is the weight part of solid content of each component.
[364] * 4) Solubility of the solvent in water: The amount of the solvent (part by weight) dissolved in 100 parts by weight of water at 20 ° C.
[365] (2) Preparation of Pigment Dispersion
[366] The pigment and the dispersant were added to the solvent, mixed, and stirred using three rolls and a bead mill to obtain a red pigment dispersion having the following composition.
[367] <Composition of Red Pigment Dispersion>
[368] . Pigment (C.I. Pigment Red 254): 5 parts by weight
[369] Dispersant (made by AVECIA, Solsperth 24000): 2 parts by weight
[370] Solvent (diethylene glycol monobutyl ether acetate): 38.3 parts by weight
[371] Solvent (propylene glycol monomethyl ether acetate): 4.7 parts by weight
[372] (3) Preparation of thermosetting ink jet ink for red pixels
[373] A rotor coated with Teflon (registered trademark) was put in a sample bottle, and it was installed in a magnetic stirrer. In this sample bottle, the said red pigment dispersion liquid and the binder composition of the said Table 3 are added, and it fully stirred and dissolved so that each component may become the mixing | blending ratio shown in Table 4, and then, a diluting solvent is added and stirred and dissolved for viscosity adjustment. Then, this was filtrated and the thermosetting inkjet ink 1-5 (solid content 20weight%, P / V ratio 0.33) for red pixels was obtained.
[374] TABLE 4
[375]
[376] * 1) The compounding ratio when the whole quantity containing a solvent is 100 weight part. However, components other than a solvent were shown by the weight which converted solid content.
[377] (4) property evaluation
[378] The obtained thermosetting ink jet inks 1 to 5 for red pixels were evaluated for stability over time (viscosity, particle diameter), dynamic viscosity, dynamic elastic modulus, and cracks.
[379] Moreover, each inkjet ink was spin-coated to the well-cleaned glass substrate, and after fully drying, the cured film with a thickness of 1 micrometer was obtained by performing final hardening at 200 degreeC for 1 hour with a hotplate. Pencil hardness, adhesiveness, and solvent resistance (color difference (DELTA) Eab) were evaluated about the obtained cured film.
[380] Evaluation Procedure of Stability over Time
[381] Immediately after preparation of each ink jet ink and after standing at 23 ° C. for one month, the viscosity and particle diameter (volume-based median diameter) were measured. The viscosity was measured by the vibration tube flow method on the conditions of the frequency 2Hz and the use tube CURRENT TUBE Tube # 1 using VILASTIC V-E SYSTEM by VILASTIC SClENTIFIC. Particle diameter (volume reference median diameter) was measured using Nikkiso Corporation MICROTRAC UPA MODEL 9230.
[382] <Evaluation Procedure of Dynamic Viscosity and Dynamic Modulus>
[383] The dynamic viscosity and dynamic elastic modulus immediately after preparation of each ink jet ink were measured by vibrating tube flow method using VILASTIC V-E SYSTEM made by VILASTIC SCIENTIFLC, under the condition of frequency 2 Hz and use tube CURRENT TUBE Tube # 1.
[384] <Evaluation Procedure of Pencil Hardness>
[385] The film obtained by using each ink jet ink was subjected to the 8.4 · 1 test method in the pencil scraping test specified in JIS K5400 (1990), and was determined to be satisfactory when exhibiting a pencil hardness of 2H or higher.
[386] <Evaluation Procedure of Adhesion>
[387] It was judged that it was favorable that the result of having performed the board | substrate tape peeling test prescribed | regulated to JlS K5400 (1990) 8.5 about the film obtained using each inkjet ink being 6 points or more.
[388] <Evaluation Procedure for Solvent Content>
[389] Color difference (ΔEab) before and after the film obtained by using each ink jet ink was immersed in N-methylpyrrolidone for 1 hour at a liquid temperature of 40 ° C. was measured. The color difference was obtained by the color difference equation of ΔEab, which was established in 1976 by the CIE. Actual measurement was performed by a microscopic spectrometer (OSP-SP100, manufactured by Olympus Kogaku Kogyo Co., Ltd.).
[390] <Presence of crack>
[391] Cracks after prebaking the coating film obtained by using each ink jet ink under the conditions of reduced pressure [150 Torr (about 19950 Pa)] under reduced pressure [150 Torr (about 19950 Pa)] for 3 minutes at 80 ° C. Observed the presence or absence.
[392] (5) Evaluation of ink jet ejection performance
[393] Using 1,2, and 3 of the above-mentioned red pixel thermosetting ink jet inks, a discharge test was conducted under conditions of an optimum voltage and a frequency of 2 kHz in the head.
[394] (6) Evaluation result
[395] Table 4 shows the aging stability (viscosity, particle diameter), dynamic viscosity, dynamic elastic modulus, pencil hardness, adhesiveness, solvent resistance (color difference ΔEab), and cracks of the inkjet inks 1-5. In particular, in the solvent resistance test, the solvent resistance (color difference ΔEab) was greatly improved by changing from a bifunctional epicoat 828 to a tetrafunctional epicoat 157 as a polyfunctional epoxy resin.
[396] In the ink jet ejection test, all of the ink jet inks 1 to 5 were ejectable. Among them, the blending ratio of the main polymer (A'-1) having a higher molecular weight than that of the inkjet ink (1) having a higher blending ratio of the main polymer (A'-1) having a higher molecular weight, and that of the multifunctional epoxy resin (C) The ink droplets of the ink jet ink 3 having a relatively high blending ratio were easily broken, and the ejection state was stable. The discharge state of the ink jet ink 1 is shown in the photograph of FIG. 8, and the discharge state of the ink jet ink 3 is shown in the photograph of FIG. It is clear from both photographs that the ink jet ink 3 is more stably ejected than the ink jet ink 1.
[397] The ink jet ink 4 has a lower compounding ratio of the main polymer (A'-1) and a higher compounding ratio of the polyfunctional epoxy resin (C) than the ink jet ink 3, but the point of discharge performance is high. Was the same as the ink jet ink 3. However, since the ink jet ink 3 uses the bifunctional epoxy resin (C), the ink jet ink 4 uses the tetrafunctional epoxy resin (C), so that the coating film properties are improved. . Specifically, the solvent resistance of the ink jet ink 4 was superior to the ink jet ink 3 among the three evaluation items (pencil hardness, adhesiveness, solvent resistance) shown in Table 4 regarding the coating film physical properties.
[398] As to the presence or absence of cracks, the other inkjet inks (1 to 4) containing the main polymer (A'-1) using methyl methacrylate (MMA) as the copolymerization monomer are cracks in the coating film under high temperature prebaking conditions. On the other hand, the inkjet ink 5 in which the main polymer (A'-2) using methoxyethyl acrylate (MEA) was used as the copolymerization monomer did not cause cracks in the coating film even under high temperature prebaking conditions.
[399] As described above, the ink jet ink composition for color filters according to the present invention does not dry rapidly even when performing intermittent ejection or continuous ejection, so that a sudden increase in viscosity at the tip of the nozzle of the ink jet head It is hard to cause clogging, and wet expansion of the orifice periphery surface is unlikely to occur, and the discharge direction and the discharge amount are excellent in stability. Therefore, by using the ink composition of the present invention, the ink jet method is ejected to the substrate surface in accordance with a predetermined pattern, whereby fine colored cured layers such as the pixel portion and the black matrix layer can be formed accurately and uniformly.
[400] Moreover, although the inkjet ink composition for color filters which concerns on this invention does not dry rapidly at the nozzle tip of an inkjet head, it has appropriate drying property. Therefore, after being discharged onto the substrate, it can be well fused to the substrate surface and sufficiently leveled, and then completely dried in a relatively short time by natural drying or a general heating method. Therefore, a pattern with high uniformity or flatness can be obtained and can be dried efficiently.
[401] In addition, in the present invention, in order to obtain a coating film having a uniform film thickness or a flat surface, the coating film of the ink composition is 100 ° C. or more, and at a temperature at which the block portion of the carboxyl group compound is not dissociated, and no dolby is generated. It is preferable to carry out prebaking by heating to the temperature of 160 degreeC or less, and after that, heating temperature is raised beyond the dissociation temperature of a carboxyl group block compound, and a postbaking is performed, and the cured film with high flatness is obtained.
[402] And when performing such high temperature prebaking and postbaking, the ink composition which mix | blended the carboxy group block compound (B) by the main polymer (A ') and / or primary alkylvinyl ether whose Tg is 70 degrees C or less is carried out. Since the occurrence of cracks can be prevented by using, a cured film having high flatness and no cracks is obtained.
[403] In addition, by selectively changing the wettability in a predetermined region of the substrate surface, an ink layer forming region having a larger ink ink relative to the surroundings is formed, and when the ink composition according to the present invention is sprayed by an ink jet method, a certain amount of The ink droplets are concentrated at the correct position, and the impacted ink droplets do not stay in the impact position and are wetted and widened to every corner of the ink layer forming region, and also the ink droplets do not protrude from the boundary line with the surrounding ink repellent region. Swell Therefore, a thick colored cured layer can be formed accurately, and for example, a pixel portion without color dropout and satisfying a desired color density and luminance is obtained.
[404] In particular, a wettability variable layer for changing the wettability in a direction in which the affinity for ink is increased by the action of the photocatalyst is formed on the substrate, and the wettability variable layer is exposed in a predetermined pattern to form the ink-inkable ink layer formation region. In this case, using the standard solution indicated in the wettability test specified in JIS K6768 as the main solvent, the contact angle (θ) after 30 seconds was measured by contacting the droplets, and the critical surface tension determined by the graph of the Gisman plot was 30 mN / using the ink composition prepared using the contact angle with respect to the surface of the test piece whose m is 25 degrees or more, and the contact angle with respect to the surface of the test piece whose critical surface tension obtained by the same measuring method is 70 mN / m is 10 degrees or less. It is desirable to obtain a precise and uniform pattern with good efficiency.
[405] According to the ink composition and the color filter manufacturing method according to the present invention, a color filter having good performance can be produced, and in particular, a pixel portion that satisfies a desired color density and luminance and is uniform and further has no color dropout can be precisely formed. The value in use is high.
[406] Moreover, the ink composition which concerns on this invention is excellent also in stability of long-term storage, and is easy to handle.

权利要求:
Claims (33)
[1" claim-type="Currently amended] (A) an epoxy compound having two or more epoxy groups in one molecule, and
(B) Formula 1 (a) or Formula 1 (b)
[Formula 1 (a)]
[Formula 1 (b)]
(R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each 1 to 18 carbon atoms). Y ¹ and Y ^{1 ′} are each an oxygen atom or a sulfur atom, and R ³ and R ⁴ may be bonded to each other to form a heterocycle in which Y ¹ is a hetero atom. R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and Y ^{1 ′} may be the same as R ¹ , R ² , R ³ and Y ¹ to which they correspond, respectively). An ink jet ink composition for color filters, containing as an essential component.
[2" claim-type="Currently amended] The method of claim 1,
The epoxy compound (A) is
(A ′) at least a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3)
[Formula 2]
(R ⁶ is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R ⁷ is a hydrocarbon group of 1 to 12 carbon atoms or-(R ⁸ X) _n -R ^9. R ⁸ is a substituted or unsubstituted C 1 to A divalent hydrocarbon group of 5, X is an oxygen atom or a sulfur atom, and R ⁹ is a C1-C12 hydrocarbon group R ⁸ and R ⁹ are bonded to each other to form a hetero atom; It may form a summon, and n is an integer of 1-10.)
[Formula 3]
(R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
An ink jet ink composition for color filters, comprising: a main polymer composed of two or more glycidyl groups.
[3" claim-type="Currently amended] The method of claim 2,
In the main polymer (A '), R ⁷ of the structural unit represented by the formula (2) is-(R ⁸ X) _n -R ⁹ , R ⁸ is a divalent hydrocarbon group having 1 to 3 carbon atoms, and X is an oxygen atom R ⁹ is an alkyl group having 1 to 3 carbon atoms, n is an integer of 1 to 5, and R ¹⁰ of the structural unit represented by the formula (3) is a hydrogen atom or a methyl group.
[4" claim-type="Currently amended] The method of claim 2,
The ink jet ink composition for color filters, wherein the weight average molecular weight of the main polymer (A ') is 10,000 or less.
[5" claim-type="Currently amended] The ink jet ink composition for color filters according to claim 1 is dissolved or dispersed in a solvent (E), wherein the ink jet ink composition for color filters is used.
[6" claim-type="Currently amended] The method of claim 5,
The solvent (E) is a main solvent having a boiling point of 180 ° C. to 260 ° C. and a solvent component having a vapor pressure of 133 Pa or less at room temperature in a proportion of 80% by weight or more relative to the total amount of the solvent (E). An ink jet ink composition for color filters, characterized by containing.
[7" claim-type="Currently amended] The method of claim 6,
As the main solvent, the standard solution presented in the wettability test specified in JIS K6768 was used, the droplets were contacted, the contact angle θ was measured after 30 seconds, and was determined by the graph of the Jisman plot. The contact angle with respect to the surface of the test piece whose critical surface tension is 30 mN / m shows 25 degrees or more, and the contact angle with the surface of the test piece whose critical surface tension is 70 mN / m determined by the same measuring method is 10 degrees or less. An ink jet ink composition for color filters, characterized by using a solvent.
[8" claim-type="Currently amended] The method of claim 6,
The main solvent is a color filter ink jet ink composition, characterized in that the solvent does not contain a hydroxyl group.
[9" claim-type="Currently amended] The method of claim 8,
The main solvent is ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dibutyl malonate, diethyl malonate And dimethyl succinate or diethyl succinate, wherein the ink jet ink composition for color filters is used.
[10" claim-type="Currently amended] The method of claim 9,
The main solvent is diethylene glycol monobutyl ether acetate, the ink jet ink composition for a color filter.
[11" claim-type="Currently amended] (C) An ink jet ink composition for color filters, further comprising a polyfunctional epoxy resin having two or more epoxy groups in one molecule.
[12" claim-type="Currently amended] The method of claim 11,
The epoxy compound (A) is
(A ′) at least a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3)
[Formula 2]
(R ⁶ is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R ⁷ is a hydrocarbon group of 1 to 12 carbon atoms or-(R ⁸ X) _n -R ^9. R ⁸ is a substituted or unsubstituted C 1 to A divalent hydrocarbon group of 5, X is an oxygen atom or a sulfur atom, R ⁹ is a hydrocarbon group of 1 to 12 carbon atoms, R ⁸ and R ⁹ are bonded to each other to form a heterocycle in which X is a hetero atom; And n is an integer of 1 to 10.)
[Formula 3]
(R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
A main polymer composed of two or more glycidyl groups, 10 to 80 parts by weight of the main polymer (A '), 10 to 60 parts by weight of the carboxyl group compound (B), and the polyfunctional epoxy An ink jet ink composition for color filters, comprising a resin (C) in a proportion of 10 to 60 parts by weight.
[13" claim-type="Currently amended] The method of claim 12,
Reaction Equivalent / Epoxy Group of Equivalent Ratios of Functional Groups of Formulas 1 (a) and 1 (b) Present in the Color Filter Inkjet Ink Composition (Equation 1 (a) or Formula 1 (b) The equivalent) is 0.2-2.0, The inkjet ink composition for color filters.
[14" claim-type="Currently amended] The method of claim 11,
The weight average molecular weight of the said main polymer (A ') is 10,000 or less, and the said polyfunctional epoxy resin (C) is a multifunctional epoxy resin of four or more functions, The inkjet ink composition for color filters.
[15" claim-type="Currently amended] The method of claim 1,
An ink jet ink composition for a color filter, wherein the carboxyl group compound (B) is a monocyclic aromatic carboxylic acid derivative represented by the following formula (5).
[Formula 5]
(F3 is a functional group represented by formula (1) or formula (1), and m is an integer of 2 or more.
[16" claim-type="Currently amended] The method of claim 15,
An ink jet ink composition for a color filter, wherein the monocyclic aromatic carboxylic acid derivative is a block of trimesic acid and / or trimellitic acid.
[17" claim-type="Currently amended] The method of claim 1,
(D) An ink jet ink composition for color filters, further comprising a thermal latent catalyst that exhibits activity upon thermal curing.
[18" claim-type="Currently amended] The method of claim 17,
The ink jet ink composition for a color filter, wherein the thermal latent catalyst (D) is a (D ′) halogen-free acidic catalyst.
[19" claim-type="Currently amended] The method of claim 1,
An ink jet ink composition for color filters, further comprising a pigment.
[20" claim-type="Currently amended] A pigment dispersion is prepared by mixing a pigment and, if necessary, a pigment dispersant as a main solvent, a dispersion preparation solvent containing a solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure at room temperature of 133 Pa or less to prepare a pigment dispersion. Sieve, (A) an epoxy compound having two or more epoxy groups in one molecule, (B) the following general formula (1) or (1)
[Formula 1 (a)]
[Formula 1 (b)]
(R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each an organic group having 1 to 18 carbon atoms). , Y ¹ and Y ^{1 'are} independently an oxygen atom or a sulfur atom. R ³ and R ⁴ may form a heterocyclic ring, which hetero atom of Y ¹ bonded to each other. ^{Further, R 1', R 2 '} , R ^{3 '} and Y ^1' may be the same as R ¹ , R ² , R ³ and Y ¹ to which they respectively correspond.) A carboxyl group compound having two or more functional groups and other components, if necessary, A method of manufacturing an ink jet ink composition for a color filter, characterized by mixing the newly prepared main solvent and adjusting the blending ratio of the main solvent to the total amount of the solvent to 80% by weight or more.
[21" claim-type="Currently amended] The method of claim 20,
As the epoxy compound (A),
(A ′) at least a structural unit represented by the following formula (2) and a structural unit represented by the following formula (3)
[Formula 2]
(R ⁶ is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, R ⁷ is a hydrocarbon group of 1 to 12 carbon atoms or-(R ⁸ X) _n -R ^9. R ⁸ is a substituted or unsubstituted C 1 to A divalent hydrocarbon group of 5, X is an oxygen atom or a sulfur atom, R ⁹ is a hydrocarbon group of 1 to 12 carbon atoms, R ⁸ and R ⁹ are bonded to each other to form a heterocycle in which X is a hetero atom; And n is an integer of 1 to 10.)
[Formula 3]
(R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
A method for producing an ink jet ink composition for color filters comprising a main polymer having two or more glycidyl groups.
[22" claim-type="Currently amended] The method of claim 20,
A method for producing an ink jet ink composition for a color filter, wherein a solvent containing no hydroxyl group is used as the main solvent.
[23" claim-type="Currently amended] The method of claim 22,
As the main solvent, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dibutyl ether, diethyl adipate, dibutyl oxalate, dibutyl malonic acid, di malonic acid Ethyl, dimethyl succinate, or diethyl succinate, The inkjet ink composition manufacturing method for color filters characterized by the above-mentioned.
[24" claim-type="Currently amended] The method of claim 23, wherein
A diethylene glycol monobutyl ether acetate is used as said main solvent, The ink jet ink composition manufacturing method for color filters characterized by the above-mentioned.
[25" claim-type="Currently amended] (1) (A) an epoxy compound having two or more epoxy groups in one molecule, and (B) the following general formula (1) or (1)
[Formula 1 (a)]
[Formula 1 (b)]
(R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each an organic group having 1 to 18 carbon atoms). , Y ¹ and Y ^{1 'are} independently an oxygen atom or a sulfur atom. R ³ and R ⁴ may form a heterocyclic ring, which hetero atom of Y ¹ bonded to each other. ^{Further, R 1', R 2 '} , R ^{3 '} and Y ^1' may be the same as R ¹ , R ² , R ³ and Y ¹ to which they respectively correspond.) For color filters containing as essential components a carboxyl group compound having at least two functional groups Preparing a inkjet ink composition;
(2) forming a ink layer by selectively attaching the ink jet ink composition for color filters to a predetermined region on a substrate by an ink jet method;
(3) heating the ink layer to form a cured layer
Color filter manufacturing method comprising a.
[26" claim-type="Currently amended] The method of claim 25,
An ink layer is formed using the inkjet ink composition for color filters containing a pigment, and the said ink layer is heated to form a colored hardened layer, The color filter manufacturing method characterized by the above-mentioned.
[27" claim-type="Currently amended] The method of claim 26,
The pixel part is formed as said colored hardening layer, The color filter manufacturing method characterized by the above-mentioned.
[28" claim-type="Currently amended] (1) An epoxy compound having two or more epoxy groups in one molecule of (A), (B) the following general formula (1) or (1)
[Formula 1 (a)]
[Formula 1 (b)]
(R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each an organic group having 1 to 18 carbon atoms). , Y ¹ and Y ^{1 'are} independently an oxygen atom or a sulfur atom. R ³ and R ⁴ may form a heterocyclic ring, which hetero atom of Y ¹ bonded to each other. ^{Further, R 1', R 2 '} , R ^{3 '} and Y ^1' may be the same as R ¹ , R ² , R ³ and Y ¹ to which they respectively correspond.) For color filters containing as essential components a carboxyl group compound having at least two functional groups Preparing a inkjet ink composition;
(2) a step of selectively changing the wettability in a predetermined region on the surface of the substrate to form an ink layer forming region having a larger ink ink than the surroundings;
(3) forming an ink layer by selectively attaching the ink jet ink composition for color filters to the ink layer forming region by an ink jet method;
(4) a step of forming a cured layer by heating the ink layer
Color filter manufacturing method comprising a.
[29" claim-type="Currently amended] The method of claim 28,
An ink layer is formed using the inkjet ink composition for color filters containing a pigment, and the said ink layer is heated to form a colored hardened layer, The color filter manufacturing method characterized by the above-mentioned.
[30" claim-type="Currently amended] The method of claim 29,
The pixel part is formed as said colored hardening layer, The color filter manufacturing method characterized by the above-mentioned.
[31" claim-type="Currently amended] (1) An epoxy compound having two or more epoxy groups in one molecule of (A), (B) the following general formula (1) or (1)
[Formula 1 (a)]
[Formula 1 (b)]
(R ¹ , R ² , R ³ , R ^{1 ′} , R ^{2 ′} and R ^{3 ′} are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ and R ⁵ are each an organic group having 1 to 18 carbon atoms). , Y ¹ and Y ^{1 'are} independently an oxygen atom or a sulfur atom. R ³ and R ⁴ may form a heterocyclic ring, which hetero atom of Y ¹ bonded to each other. ^{Further, R 1', R 2 '} , R ^{3 '} and Y ^1' may be the same as R ¹ , R ² , R ³ and Y ¹ to which they respectively correspond.) A carboxyl group compound having two or more functional groups represented by R &lt; ¹ &gt; Vapor pressure at 260 ° C and room temperature is 133 Pa or less, and using the standard solution presented in the wettability test prescribed in JIS K6768, the contact angle (θ) after 30 seconds was measured by contacting the droplets, Critical surface obtained by the same measuring method as the contact angle with respect to the surface of the test piece whose critical surface tension is 30 mN / m was 25 degrees or more Inkjet ink composition for color filters containing as an essential component a solvent containing a main solvent having a contact angle of 10 ° or less to a surface of a test piece having a tension of 70 mN / m in a proportion of 80% by weight or more with respect to the total amount of the solvent components. To prepare the process,
(2) forming a wettability variable layer capable of changing wettability in a direction in which affinity of ink is increased by the action of a photocatalyst on a substrate;
(3) a step of selectively changing the wettability in a predetermined region of the surface of the wettability variable layer by exposure to form an ink layer forming region having a larger ink ink than the surroundings;
(4) forming an ink layer by selectively attaching the ink jet ink composition for color filters to the ink layer region by an ink jet method;
(5) a step of heating the ink layer to form a cured layer
Color filter manufacturing method comprising a.
[32" claim-type="Currently amended] The method of claim 31, wherein
An ink layer is formed using the inkjet ink composition for color filters containing a pigment, and the said ink layer is heated to form a colored hardened layer, The color filter manufacturing method characterized by the above-mentioned.
[33" claim-type="Currently amended] 33. The method of claim 32,
The pixel part is formed as said colored hardening layer, The color filter manufacturing method characterized by the above-mentioned.

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同族专利:

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公开号 | 公开日

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EP1266943A2|2002-12-18|

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EP1266943A3|2003-10-29|

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EP1266943B1|2007-07-18|

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CN1392204A|2003-01-22|

---

JP2003066223A|2003-03-05|

---

US7470730B2|2008-12-30|

---

CN100396739C|2008-06-25|

---

KR100922539B1|2009-10-21|

---

US20040048950A1|2004-03-11|

---

JP4202680B2|2008-12-24|

---

DE60221192D1|2007-08-30|

---

DE60221192T2|2008-04-10|

---

TWI247785B|2006-01-21|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-06-15|Priority to JPJP-P-2001-00182566

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2001-06-15|Priority to JP2001182566

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2002-06-06|Priority to JP2002166359A

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2002-06-06|Priority to JPJP-P-2002-00166359

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2002-06-14|Application filed by 다이니폰 인사츠 가부시키가이샤, 닛폰 유시 가부시키가이샤

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2002-12-31|Publication of KR20020096909A

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2009-10-21|Application granted

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2009-10-21|Publication of KR100922539B1

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2001-00182566|2001-06-15|

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JP2001182566|2001-06-15|

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JP2002166359A|JP4202680B2|2001-06-15|2002-06-06|Ink-jet ink composition for color filter, method for producing ink composition, and method for producing color filter|

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JPJP-P-2002-00166359|2002-06-06|