Radiation Sensitive Composition and Colored Layer for Color Liquid Crystal Display Device, and Color

专利摘要:
PURPOSE: To provide a radiation sensitive composition for a color liquid crystal display device which is used to form a color layer on a driving substrate of a color liquid crystal display device with a thin film transistor(TFT) method and which shows such properties that no seizure of an image is caused during operating the display panel, conducting paths of <= 5 μm length can be formed, no development residue is produced during development and excellent adhesion property with the driving substrate or a passivation film is obtained. CONSTITUTION: The radiation sensitive composition for a color liquid crystal display device contains (A) pigments, (B) dispersant, (C) alkali soluble resin (D) polyfunctional monomers and (E) photopolymerization initiator. The extracted amount of the caprolacton component in a color layer formed from the above composition by acetonitrile is <= 5 wt.% of the color layer. The composition is to be used to form a color layer on the driving substrate of a color liquid crystal display device with a thin film transistor(TFT) method.
公开号:KR20020010085A
申请号:KR1020010045034
申请日:2001-07-26
公开日:2002-02-02
发明作者:히데유끼 가미이；히데또시 미야모또；도미오 나가쯔까；쯔요시 와따나베
申请人:마쯔모또 에이찌；제이에스알 가부시끼가이샤；
IPC主号:

专利说明:

Radiation sensitive composition and colored layer for color liquid crystal display device, and color liquid crystal display element}
[1] The present invention provides a radiation sensitive material for a color liquid crystal display device used to form a colored layer including a pixel and / or a black matrix of a color liquid crystal display device on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. A composition, and a color liquid crystal display device.
[2] In a color liquid crystal display device using a thin film transistor (TFT) substrate, conventionally, a color filter substrate for displaying a color image is manufactured separately from a driving substrate on which a thin film transistor (TFT) is disposed, and the color filter substrate is described above. It was manufactured by bonding to a driving substrate. However, in this system, since the positional accuracy at the time of joining is low, the width | variety of a black matrix must be enlarged and it is difficult to raise aperture ratio (namely, the ratio of the opening which permeate | transmits light).
[3] On the other hand, with respect to the above method, a colored layer is formed on the surface of the driving substrate on which the thin film transistor (TFT) is arranged, either directly or through a passivation film such as a silicon nitride film, and the substrate on which the colored layer is formed is formed by ITO (tin). A method of bonding an indium oxide (doped indium oxide) electrode to a substrate formed thereon has been developed. In this method, since a colored layer including a pixel or a black matrix is formed directly on the driving substrate, the bonding process between the color filter substrate and the driving substrate is unnecessary, and the aperture ratio can be greatly improved as compared with the former method. It is possible to obtain a bright and high precision display device.
[4] However, when the colored layer is formed by the latter method, image baking tends to occur during operation of the display panel, which is a big problem. Although the impurity which leaked into the liquid crystal from the colored layer can be considered as the cause, the kind of the impurity which is applicable is not necessarily clear, and the evaluation criteria which can effectively prevent image baking are also unclear. It is becoming.
[5] Further, the colored layer formed by this method has a rectangular through hole or c-shaped of about 1 to 15 µm in length and preferably 5 µm or less in order to conduct the ITO electrode disposed on the colored layer and the driving substrate terminal under the colored layer. It is necessary to form a conductive path such as a recess, but in a radiation-sensitive composition used for forming a colored layer on a driving substrate of a conventional thin film transistor (TFT) type color liquid crystal display device, a conduction of 5 μm or less is particularly preferable. The furnace could not be formed.
[6] In addition, in such a liquid crystal display device, it is necessary to form electrodes on the pixels, and therefore, when the pixel shape becomes an inverse tapered shape, the electrodes formed on the pixels are disconnected and display defects such as pixel defects may occur. It was a problem.
[7] SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and the problem is that the conductive path of 5 µm or less can be formed without causing image baking during display panel operation, and a pure tapered pixel can be formed. In addition, no development residue is generated during development, and a thin film transistor (TFT) type color liquid crystal display device having excellent adhesion and surface smoothness with a passivation film such as a silicon nitride film and a driving substrate on which a thin film transistor (TFT) is disposed is also driven. It is providing the radiation sensitive composition for color liquid crystal display devices used for forming a colored layer on the board | substrate for solvents.
[8] According to this invention, the said subject is a radiation sensitive composition for color liquid crystal display devices containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, Comprising: The amount of extraction of the caprolactone component by acetonitrile of the colored layer is 5% by weight or less of the colored layer, which is used to form a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device. It is achieved by the radiation sensitive composition for color liquid crystal display devices.
[9] In addition, according to the present invention,
[10] (1) forming a coating film of the radiation-sensitive composition for a color liquid crystal display device described above on a TFT system liquid crystal drive substrate;
[11] (2) It is achieved by the manufacturing method of the color filter characterized by including the process of exposing at least one part of the said coating film, and then developing.
[12] The said subject is also achieved by the colored layer for color liquid crystal display devices formed from the radiation sensitive composition for color liquid crystal display devices.
[13] Moreover, the said subject is achieved by the liquid crystal display element in which the colored layer for color liquid crystal display devices was formed on the drive board | substrate of a thin film transistor (TFT) system color liquid crystal display device.
[14] "Caprolactone component" as used in the present invention means caprolactone, caprolactone derivatives, or a mixture of two or more thereof.
[15] In addition, the term "radiation" in the present invention means that it includes visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.
[16] The present inventors earnestly examined about the impurity which causes image baking at the time of operation of a display panel, and the evaluation criteria which can effectively prevent image baking, As a result, the caprolactone component which oozes out into a liquid crystal from a colored layer causes image baking. It is a great cause, and it discovered that image baking can be prevented effectively by setting the extraction amount of the caprolactone component by the acetonitrile of a colored layer to 5 weight% or less of the said colored layer, and came to complete this invention.
[17] Therefore, in all the components which comprise the radiation sensitive composition for color liquid crystal display devices of this invention, especially the (B) dispersing agent, content of the caprolactone component is "zero (0)" or it is preferable as few as possible. In this case, as a caprolactone derivative in a caprolactone component, the methyl substituent of caprolactone, the oligomer of caprolactone, and the methyl substituent (polymerization degree is 4 or less, for example) etc. are mentioned, for example.
[18] Moreover, when a significant amount of caprolactone component is contained with respect to any component which comprises the radiation sensitive composition for color liquid crystal display devices of this invention, the total amount of the polymerizable unsaturated bond in a polyfunctional monomer (A) is (A) It is preferable to make into a predetermined value the ratio which occupies for the sum total of (D) component.
[19] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
[20] (A) colorant
[21] The coloring agent of this invention is not specifically limited in color tone, According to the use of the color filter obtained, it is suitably selected, It can be any of a pigment, dye, or a natural pigment.
[22] Since the color filter requires high color development and heat resistance, the colorant of the present invention is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance, and is usually a pigment, particularly preferably an organic pigment and / or ) Carbon black is used.
[23] Examples of the organic pigments include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists, Inc.), specifically those having the following color index (CI) numbers. Can be.
[24] CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 211;
[25] C.I. Pigment Orange 36, C.I.Pigment Orange 43, C.I.Pigment Orange 51, C.I.Pigment Orange 61, C.I.Pigment Orange 71;
[26] CI Pigment Red 9, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, CI Pigment CI Pigment Red 180, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254;
[27] C.I. Pigment Violet 19, C.I.Pigment Violet 23, C.I.Pigment Violet 29;
[28] C. I. Pigment Blue 15, C. I. Pigment Blue 60, C. I. Pigment Blue 15: 3, C. I. Pigment Blue 15: 4, C. I. Pigment Blue 15: 6;
[29] C.I. pigment green 7, C.I. pigment green 36, C.I. pigment green 136, C.I. pigment green 210;
[30] C.I. Pigment Brown 23, C.I.Pigment Brown 25;
[31] C.I. Pigment Black 1, C.I.Pigment Black 7.
[32] These organic pigments can be used individually or in mixture of 2 or more types.
[33] Moreover, the said organic pigment can also be refine | purified and used by the recrystallization method, the reprecipitation method, the solvent washing method, the sublimation method, the vacuum heating method, and a combination thereof.
[34] Specific examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zincation, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide (III)), cadmium, ultramarine blue, bluish orange oxide, chromium oxide, cobalt rust, Amber, titanium black, synthetic iron black, carbon black, etc. are mentioned.
[35] These inorganic pigments can be used individually or in mixture of 2 or more types.
[36] When the radiation sensitive composition for a color liquid crystal display device in the present invention is used to form a pixel, preferably at least one organic pigment is used as a colorant, and when used to form a black matrix, preferably as a colorant. Two or more organic pigments and / or carbon blacks are used.
[37] In the present invention, each of the pigments can be used by modifying the particle surface of the polymer according to the purpose. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, etc., a commercially available pigment dispersion polymer, or oligomer etc. are mentioned, for example.
[38] When using a pigment as a coloring agent in this invention, it is preferable to use a dispersing agent. A dispersant is a component which functions to disperse a pigment uniformly in a radiation sensitive composition.
[39] Examples of such dispersants include dispersants such as cationic, anionic, nonionic, amphoteric, silicone, and fluorine-based compounds.
[40] Examples of the dispersant include dispersants having a urethane bond (hereinafter referred to as "urethane dispersant"); Polyethyleneimine-based dispersants; Polyoxyethylene alkyl ether dispersants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ether dispersants such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyethylene glycol diester dispersants such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid ester-based dispersants; And fatty acid-modified polyester-based dispersants.
[41] Among these dispersants, urethane-based dispersants are particularly preferable. The urethane-based dispersant contains very little or no caprolactone component which causes burn baking.
[42] As a commercial item of the said preferable dispersing agent, For example, Disperbyk (made by Big Chemie Japan Co., Ltd.) and EFKA (made by EFKA Co., Ltd.) ), Disperon (Kusumoto Kasei Co., Ltd.), etc. are mentioned.
[43] In this invention, a dispersing agent can be used individually or in mixture of 2 or more types.
[44] The use amount of the dispersant of the present invention is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the pigment. In this case, when the usage-amount of a dispersing agent exceeds 100 weight part, developability etc. may be impaired.
[45] Moreover, in this invention, a dispersal aid can also be used together with the said dispersing agent.
[46] As said dispersing adjuvant, a copper phthalocyanine sulfonic-acid compound etc. are mentioned, for example.
[47] Specific examples of the copper phthalocyanine sulfonic acid compound include copper phthalocyanine sulfonic acid, copper phthalocyanine sulfonic acid ammonium, copper phthalocyanine sulfonic acid tetramethylammonium, copper phthalocyanine sulfonic acid tetraethylammonium, copper phthalocyanine sulfonic acid tetra-n-propyl ammonium, copper phthalocyanine sulfonic acid tetra-i-propyl ammonium And copper phthalocyanine sulfonic acid tetra-n-butylammonium.
[48] These copper phthalocyanine sulfonic acid compounds can be used individually or in mixture of 2 or more types.
[49] The use amount of the dispersing aid is usually 20 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the pigment.
[50] (B) alkali soluble resin
[51] As alkali-soluble resin in this invention, if it acts as a binder with respect to (A) coloring agent, and it is soluble with respect to the developing solution used by the developing process at the time of manufacturing a color filter, especially preferably alkaline developing solution, it will be specifically limited. Although not mentioned, the copolymer of the polymerizable unsaturated monomer which has acidic functional groups, such as a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid, and another copolymerizable unsaturated monomer (henceforth "copolymerizable unsaturated monomer") is mentioned.
[52] As a polymerizable unsaturated monomer which has a carboxyl group (henceforth "a carboxyl group-containing unsaturated monomer"), for example,
[53] Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;
[54] Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or anhydrides thereof;
[55] Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;
[56] Mono [(meth) acryloyloxyalkyl] of divalent or more polyvalent carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;
[57] and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as -carboxypolycaprolactone mono (meth) acrylate.
[58] Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl] and the like are particularly preferable.
[59] The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.
[60] As the polymerizable unsaturated monomer having a phenolic hydroxyl group, for example, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, o-hydroxy-α-methylstyrene, m-hydroxy-α- Methyl styrene, p-hydroxy- (alpha)-methylstyrene, No-hydroxyphenyl maleimide, Nm-hydroxyphenyl maleimide, Np-hydroxyphenyl maleimide, etc. are mentioned.
[61] The polymerizable unsaturated monomer which has such a phenolic hydroxyl group can be used individually or in mixture of 2 or more types.
[62] Moreover, isoprene sulfonic acid, p-styrene sulfonic acid, etc. are mentioned as a polymerizable unsaturated monomer which has a sulfonic acid group, for example.
[63] The polymerizable unsaturated monomer which has such a sulfonic acid group can be used individually or in mixture of 2 or more types.
[64] Subsequently, as a copolymerizable unsaturated monomer, for example,
[65] Macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane (hereinafter, simply referred to as "macromonomer") N-phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide N-position substituted maleimide, such as N- (substituted) aryl maleimide, such as the mead, and N-cyclohexyl maleimide;
[66] Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;
[67] Indenes such as indene and 1-methylindene;
[68] Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxy propylene glycol (meth) acrylate, Toxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth Unsaturated carboxylic acid esters such as acrylate;
[69] 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, 3 Unsaturated carboxylic acid aminoalkyl esters such as -dimethylaminopropyl (meth) acrylate;
[70] Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
[71] Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;
[72] Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;
[73] Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;
[74] Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl (meth) acrylamide;
[75] And aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.
[76] These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.
[77] Of the copolymerizable unsaturated monomers, macromonomers, N-position substituted maleimides, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, and glycerol (meth) acrylate are preferable. Moreover, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer are especially preferable among macromonomers, and N-phenylmaleimide and N-cyclohexyl maleimide are especially preferable among N-position substituted maleimides.
[78] Preferred alkali-soluble resins of the present invention include copolymers of carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers (hereinafter, simply referred to as "carboxyl group-containing copolymers").
[79] Examples of the carboxyl group-containing copolymer include (1) a carboxyl group-containing unsaturated monomer, (2) a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, and 2-hydroxyethyl (meth) acrylate. , Benzyl (meth) acrylate and glycerol (meth) acrylate, at least one selected from the group, ③ optionally styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylic Copolymers of the monomer mixture further containing one or more selected from the group of the rates (hereinafter referred to as "carboxyl group-containing copolymer (I)") are preferable, and in particular, (1) (meth) acrylic acid is an essential component, And a carboxyl group-containing unsaturated monomer component further containing succinic acid mono [2- (meth) acryloyloxyethyl], ② polystyrene macromonomer, poly Methyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate (3) a copolymer of a monomer mixture containing at least one, and optionally further comprising at least one selected from the group of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. (Hereinafter, referred to as "carboxyl group-containing copolymer (II)") is preferable.
[80] As a specific example of carboxyl group-containing copolymer (II),
[81] (Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
[82] (Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
[83] (Meth) acrylic acid / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,
[84] (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer,
[85] (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer,
[86] (Meth) acrylic acid / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,
[87] (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer,
[88] (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / benzyl (meth) acrylate / styrene copolymer,
[89] (Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
[90] (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
[91] (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer,
[92] (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / styrene copolymer,
[93] (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
[94] (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
[95] (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
[96] (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
[97] (Meth) acrylic acid / N-phenylmaleimide / benzyl (meth) acrylate / glycerol mono (meth) acrylate / styrene copolymer etc. are mentioned.
[98] The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, when the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility in the alkaline developer of the resulting radiation-sensitive composition tends to decrease, while when it exceeds 50% by weight, the solubility in the alkaline developer is excessively high, resulting in an alkali developer. When it develops in this case, a colored layer tends to fall out of a board | substrate and it becomes difficult to make surface roughness of a colored layer small enough.
[99] As for polystyrene conversion weight average molecular weight (henceforth "Mw") measured by the gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of alkali-soluble resin of this invention, 3,000-300,000 are preferable, 5,000-100,000 This is more preferable.
[100] In addition, the polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin of the present invention is preferably 3,000 to 60,000, 5,000 To 25,000 are more preferred.
[101] By using an alkali-soluble resin having such specific Mw or Mn, a radiation-sensitive composition excellent in developability can be obtained, whereby a pixel having a sharp pattern edge can be formed, and also on the substrate of the unexposed part during development. And no residue, background contamination, film residue, or the like is generated on the light shielding layer.
[102] Moreover, ratio (Mw / Mn) of Mw and Mn of alkali-soluble resin of this invention is 1-5 normally, Preferably it is 1-4.
[103] In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
[104] The use amount of alkali-soluble resin in this invention is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, when the amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may be lowered, or background contamination and film residue may occur on the substrate or the light shielding layer of the unexposed part, while 1,000 weight When the portion is exceeded, the colorant concentration decreases relatively, so that it may be difficult to achieve the desired color concentration as a thin film.
[105] (C) polyfunctional monomer
[106] The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
[107] As an example of a polyfunctional monomer,
[108] Diacrylates or dimethacrylates of alkylene glycols such as ethylene glycol and propylene glycol;
[109] Diacrylates or dimethacrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
[110] Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and dicarboxylic acid modified substances thereof;
[111] Oligoacrylates or oligomethacrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins and spiran resins;
[112] Diacrylates or dimethacrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone, and
[113] Tris (2-acryloyloxyethyl) phosphate, a tris (2-methacryloyl oxyethyl) phosphate, etc. are mentioned.
[114] Among these polyfunctional monomers, polyacrylates or polymethacrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances are preferable, and specifically, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate. , Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipenta Erythritol hexaacrylate, dipentaerythritol hexamethacrylate, the compound represented by following formula (1), etc. are preferable, and trimethylol propane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate are especially preferable. Colored layer strength is high, colored layer table Excellent in smoothness, and it is also preferable in that the background contamination on the light-shielding layer and on the unexposed portion of the substrate, film or the like residue not occur.
[115]
[116] These polyfunctional monomers can be used individually or in mixture of 2 or more types.
[117] The usage-amount of the polyfunctional monomer of this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In addition, the total amount (mmol) of the polymerizable unsaturated bond in the (C) polyfunctional monomer is 2 to 4 mmol / g, preferably 2.5 to 3.5 mmol / g based on the total amount (g) of the components (A) to (D). to be. If the value is less than 2 mmol / g, the component may seep out from the pixel to the liquid crystal layer at the contact portion of the pixel formed from the composition with the liquid crystal, while if the value exceeds 4 mmol / g, the pixel formed from the composition The cross-sectional shape of may be inversely tapered, which is not preferable.
[118] In this invention, the monofunctional monomer which has one polymerizable unsaturated bond can also be used together with a polyfunctional monomer.
[119] As said monofunctional monomer, the carboxyl group-containing unsaturated monomer, copolymerizable unsaturated monomer, and N-vinyl succinimide, N-vinylpyrrolidone, N-vinyl phthalimide which were illustrated with respect to said (B) alkali-soluble resin, for example, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinylindole, N-vinyl induction, such as N-vinyl indolin, N-vinyl benzimidazole, N-vinylcarbazole, N-vinyl piperidine, N-vinyl pyrazine, N-vinylmorpholine, and N-vinylphenoxadine visit; In addition to N- (meth) acryloyl morpholine, M-5300, M-5400, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.
[120] These monofunctional monomers can be used individually or in mixture of 2 or more types.
[121] The use ratio of monofunctional monomer is 90 weight% or less normally with respect to the sum total of a polyfunctional monomer and a monofunctional monomer, Preferably it is 50 weight% or less. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the intensity of the pixel and the black matrix may decrease, or it may be difficult to sufficiently reduce the surface roughness of the pixel.
[122] (D) photoinitiator
[123] The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and monofunctional monomer used in some cases by irradiation (hereinafter referred to as "exposure") of visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like. It is a compound capable of generating active species capable of initiating the polymerization of.
[124] As such a photoinitiator, an acetophenone type compound, a biimidazole type compound, a triazine type compound, a benzoin type compound, a benzophenone type compound, the (alpha)-diketone type compound, a polynuclear quinone type compound, a xanthone type compound, a diazo type compound etc. Can be mentioned.
[125] In the present invention, the photopolymerization initiator may be used alone or in combination of two or more thereof. As the photopolymerization initiator in the present invention, one or more selected from the group consisting of acetophenone compounds, biimidazole compounds, and triazine compounds are preferable. .
[126] The general usage-amount of the photoinitiator in this invention is 0.01-80 weight part normally, Preferably it is 1-60 weight part with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer. In this case, when the usage-amount of a photoinitiator is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the pixel array in which a pixel pattern was arrange | positioned according to a predetermined arrangement, and when it exceeds 80 weight part, the colored layer formed This phenomenon tends to easily fall off the substrate.
[127] As a specific example of an acetophenone type compound in the preferable photoinitiator of this invention,
[128] 2-hydroxy-2-methyl-1-phenylpropan-1-one,
[129] 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,
[130] 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,
[131] 1-hydroxycyclohexyl phenyl ketone,
[132] 2, 2- dimethoxy- 1, 2- diphenyl ethane- 1-one etc. are mentioned.
[133] Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-1,2-benzyl-2-dimethylamino-1- (4-morpholino) Phenyl) butanone-1 is preferred.
[134] The acetophenone compounds may be used alone or in combination of two or more thereof.
[135] In the present invention, when the acetophenone-based compound is used as the photopolymerization initiator, the amount of use is usually 0.01 to 80 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. More preferably, it is 1-30 weight part. In this case, when the amount of the acetophenone-based compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel array in which the pixel patterns are arranged in accordance with a predetermined arrangement. The layer tends to easily fall off the substrate during development.
[136] Moreover, as a specific example of a biimidazole type compound,
[137] 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
[138] 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole,
[139] 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
[140] 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
[141] 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
[142] 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
[143] 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
[144] 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.
[145] Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 More preferred are ', 5,5'-tetraphenyl-1,2'-biimidazole, especially 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole is preferred.
[146] The biimidazole-based compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved seafood, precipitates, and the like, and further has high sensitivity, and sufficiently proceeds the curing reaction by exposure of a small amount of energy, and hardening reaction in an unexposed part. Since this does not occur, the coated film after exposure is clearly divided into an insoluble hardened portion with respect to the developer and an uncured portion with high solubility with respect to the developer, whereby a pixel of high precision with no undercut pixel patterns arranged in a predetermined arrangement An array can be formed.
[147] The said biimidazole type compound can be used individually or in mixture of 2 or more types.
[148] In the present invention, when the biimidazole-based compound is used as the photopolymerization initiator, the amount of use is usually 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. Parts, more preferably 1 to 20 parts by weight. In this case, when the amount of the non-imidazole compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel array in which pixel patterns are arranged in a predetermined arrangement. When formed, the colored layer tends to be easily detached from the substrate.
[149] Hydrogen donor
[150] When using a biimidazole type compound as a photoinitiator in this invention, using the following hydrogen donor together is preferable at the point which can improve a sensitivity further.
[151] As used herein, the term "hydrogen donor" means a compound capable of donating a hydrogen atom to radicals generated from a biimidazole compound by exposure.
[152] As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.
[153] The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one mercapto group directly bonded to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter, " Mercaptan-based hydrogen donors ".
[154] In addition, the amine compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter, "Amine hydrogen donor").
[155] Such hydrogen donors may also have a mercapto group and an amino group simultaneously.
[156] This hydrogen donor is described in more detail below.
[157] The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles, and may also have both a benzene ring and a heterocycle, and in the case of having two or more such rings, a condensed ring may or may not be formed. .
[158] In addition, when the mercaptan-based hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group as long as one or more free mercapto groups remain. Only when two or more free mercapto groups remain, the two sulfur atoms may have a structural unit bonded via a divalent organic group such as an alkylene group, or two sulfur atoms in a disulfide form.
[159] The mercaptan-based hydrogen donor may be substituted by a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a portion other than the mercapto group.
[160] Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2 Mercapto-2,5-dimethylaminopyridine and the like.
[161] Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.
[162] Subsequently, the amine-based hydrogen donor may have one or more benzene rings or heterocycles, and may also have both benzene rings and heterocycles. When two or more such rings have a condensed ring, they may or may not be formed. It may be.
[163] In the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and at a portion other than the amino group, a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group, nitrile group, It may be substituted by.
[164] Specific examples of such amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiophenone. , Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, and the like.
[165] Among these amine-based hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and particularly 4,4'-bis (diethylamino) benzophenone This is preferred.
[166] The amine-based hydrogen donor acts as a sensitizer even in the case of photopolymerization initiators other than the biimidazole-based compound.
[167] In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof, and the colored layer formed by using one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors in combination may be removed from the substrate during development. It is preferable because it does not drop off and the strength and sensitivity of the colored layer are also high.
[168] Specific examples of the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'-bis ( Diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, etc. 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone and 2-mercaptobenzooxazole / 4,4'-bis (diethylamino ) Benzophenone, particularly preferred combinations include 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.
[169] In the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor, the weight ratio of the mercaptan-based hydrogen donor and the amine-based hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.
[170] In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount of the donor is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight based on 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. Preferred, 1 to 20 parts by weight. In this case, when the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to be lowered. On the other hand, when the amount of the hydrogen donor exceeds 40 parts by weight, the formed colored layer tends to be easily removed from the substrate during development.
[171] Moreover, as a specific example of the said triazine type compound,
[172] 2,4,6-tris (trichloromethyl) -s-triazine,
[173] 2-methyl-4,6-bis (trichloromethyl) -s-triazine,
[174] 2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,
[175] 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,
[176] 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,
[177] 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine,
[178] 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,
[179] 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine,
[180] And triazine-based compounds having halomethyl groups, such as 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.
[181] Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine and the like are preferable.
[182] The said triazine type compound can be used individually or in mixture of 2 or more types.
[183] In the present invention, when the triazine-based compound is used as the photopolymerization initiator, the amount of use is preferably 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 1-20 weight part is especially preferable. In this case, when the amount of the triazine-based compound used is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel array in which the pixel patterns are arranged in accordance with a predetermined arrangement. There is a tendency to easily fall off from the substrate during this development.
[184] additive
[185] The radiation sensitive composition for color liquid crystal display devices of this invention may contain various additives as needed.
[186] The additives further improve the dissolution characteristics of the radiation-sensitive composition with respect to the alkaline developer, and further suppress the remaining of the undissolved product after development, and include organic acids or organic amino compounds (except for the hydrogen donor). Etc. can be mentioned.
[187] Organic acids
[188] As said organic acid, the aliphatic carboxylic acid or phenyl group containing carboxylic acid which has one or more carboxyl groups in molecular weight, and whose molecular weight is 1,000 or less is preferable.
[189] As an example of the said aliphatic carboxylic acid,
[190] Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, and caprylic acid;
[191] Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, subric acid, azelaic acid, sebacic acid, brasyl acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid;
[192] Aliphatic tricarboxylic acids, such as tricarvalic acid, aconitic acid, and camphoronic acid, etc. are mentioned.
[193] Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group and compounds in which the carboxyl group is bonded to a phenyl group via a carbon chain.
[194] As an example of a phenyl group containing carboxylic acid,
[195] Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid;
[196] Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;
[197] Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid, and
[198] Phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropaic acid, cinnamic acid, cinnamiledic acid, cumalic acid, unbelic acid, and the like.
[199] Among these organic acids, aliphatic dicarboxylic acids are preferable as the aliphatic carboxylic acid, from the viewpoints of alkali solubility, solubility in a solvent to be described later, prevention of background contamination and film residue on the substrate of the unexposed part or on the light shielding layer. Malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable, and as the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
[200] The said organic acid can be used individually or in mixture of 2 or more types.
[201] The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic acid exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.
[202] Organic Amino Compounds
[203] Moreover, as said organic amino compound, the aliphatic amine or phenyl group containing amine which has 1 or more amino group in a molecule | numerator is preferable.
[204] As an example of the said aliphatic amine,
[205] mono (cyclo) alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine and n-hexylamine;
[206] Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di- di (cyclo) alkylamines such as sec-butylamine and di-t-butylamine;
[207] Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri tri (cyclo) alkylamines such as -i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine and tri-t-butylamine;
[208] Mono (cyclo) alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, and 4-amino-1-butanol;
[209] Di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine and di-i-butanolamine;
[210] Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine and tri-i-butanolamine;
[211] 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2 Amino (cyclo) alkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, and 2-diethylamino-1,3-propanediol ;
[212] and aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, and 3-aminoisobutyric acid.
[213] Moreover, as a phenyl group containing amine, the compound etc. which the amino group couple | bonded with the phenyl group directly, the amino group couple | bonded with the phenyl group through the carbon chain, etc. are mentioned, for example.
[214] As an example of a phenyl group containing amine,
[215] Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p Aromatic amines such as -methyl-N, N-dimethylaniline;
[216] aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol;
[217] aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;
[218] and aminobenzoic acids (derivatives) such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.
[219] Among these organic amino compounds, mono (cyclo) alkanolamines and amino (cyclo) alkanediols are used as aliphatic amines from the viewpoint of solubility in a solvent to be described later, prevention of background contamination on the substrate or the light shielding layer of the unexposed portion, and film residue. Preferred, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol etc. are preferable, and as a phenyl group containing amine, aminophenols are preferable, and o-aminophenol, m-aminophenol, p-aminophenol, etc. are especially preferable.
[220] The said organic amino compound can be used individually or in mixture of 2 or more types.
[221] The amount of the organic amino compound to be used is usually 15% by weight or less, preferably 10% by weight or less based on the total amount of the radiation sensitive composition. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, adhesiveness with the board | substrate of the formed colored layer tends to fall.
[222] Other additives
[223] Moreover, as another additive, for example
[224] Dispersing aids such as blue pigment derivatives such as copper phthalocyanine derivatives and yellow pigment derivatives;
[225] Fillers such as glass and alumina;
[226] Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, and poly (chloroalkyl acrylates);
[227] Surfactants such as nonionic, cationic and anionic systems;
[228] Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl dimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Adhesion promoters such as oxysilane;
[229] Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol;
[230] Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones;
[231] Aggregation inhibitors such as sodium polyacrylate;
[232] And thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.
[233] menstruum
[234] The radiation sensitive composition for color liquid crystal display devices of the present invention contains the above-mentioned (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer and (D) photoinitiator as essential components, but preferably a solvent is blended. It is prepared as a liquid composition.
[235] As said solvent, (A)-(D) component and additive component which comprise a radiation sensitive composition are disperse | distributed or melt | dissolved, and it does not react with these components, It can select suitably, and can use suitably, as long as it has moderate volatility.
[236] As a specific example of such a solvent,
[237] Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n -Propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene Glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl such as propylene glycol monoethyl ether Termini and the like;
[238] (Poly) alkylenes such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates;
[239] Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;
[240] Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;
[241] Lactic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;
[242] Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 Methyl hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, acetic acid n Butyl, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate;
[243] Aromatic hydrocarbons such as toluene and xylene;
[244] Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like.
[245] When using a pigment as a solubility and a coloring agent in such a solvent, it is propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate from a viewpoint of the dispersibility, applicability | paintability, etc., Diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 2-hydroxypropionate ethyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3- Ethyl ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-butyric acid Propyl, n-butyl butyrate, ethyl pyruvate and the like are preferred.
[246] The said solvent can be used individually or in mixture of 2 or more types.
[247] In addition, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, capric acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate together with the solvent High boiling point solvents, such as diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together.
[248] The said high boiling point solvent can be used individually or in mixture of 2 or more types.
[249] The amount of the solvent used is not particularly limited, but the total concentration of each component except for the solvent of the composition is preferably 5 to 50% by weight, particularly preferably 10 to 10, in view of the coating property, stability, and the like of the resulting radiation-sensitive composition. Amounts of 40% by weight are preferred.
[250] Formation method of the colored layer
[251] The radiation-sensitive composition for a color liquid crystal display device of the present invention is formed on a driving substrate (hereinafter referred to as a "TFT type liquid crystal drive substrate") on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is disposed. It is used to form a colored layer in the lithography method. The colored layer herein means that only the display pixels, only the black matrix, or both are included.
[252] Here, the method of forming a colored layer on a TFT system liquid crystal drive board | substrate is demonstrated.
[253] A light shielding layer is formed on the surface of the TFT type liquid crystal driving substrate or on the surface of the substrate on which a passivation film such as a silicon nitride film is formed on the surface of the driving substrate so as to partition a portion for forming a pixel as necessary. After apply | coating the liquid composition of the radiation sensitive composition which red pigment disperse | distributed to, for example, it pre-bakes and evaporates a solvent and forms a coating film. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, removes and removes the unexposed part of a coating film, and post-bakes to form the pixel array in which the red pixel pattern was arrange | positioned in the predetermined | prescribed arrangement. The photomask used at this time is provided with a pattern for forming a through hole or a U-shaped recess in addition to the pattern for forming a pixel.
[254] In addition, using the liquid composition of each radiation-sensitive composition in which green or blue pigments are dispersed, and applying, prebaking, exposing, developing and postbaking each liquid composition in the same manner as above, the green pixel array and the blue pixel array By forming the film on the same substrate, it is possible to obtain a liquid crystal display element in which each pixel array of red, green, and blue is formed on a TFT type liquid crystal driving substrate. In addition, when forming a pixel array on a TFT type liquid crystal drive substrate, the order of forming each pixel array of red, green, and blue is not specifically limited.
[255] The black matrix can also be formed in the same manner as in the pixel array.
[256] As a board | substrate in the TFT system liquid crystal drive substrate used at the time of forming a colored layer, glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example. Depending on the purpose, such a substrate may be subjected to appropriate pretreatment such as chemical treatment, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like.
[257] When apply | coating the liquid composition of a radiation sensitive composition to a board | substrate, the appropriate coating methods, such as rotational coating, casting | flow_spread coating, roll coating, etc. can be employ | adopted.
[258] 0.1-10 micrometers is preferable as a film thickness after solvent removal, 0.2-5.0 micrometers is more preferable, 0.2-3.0 micrometers is especially preferable.
[259] As the radiation used for forming the colored layer, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
[260] The exposure dose of radiation is preferably 10 to 10,000 J / m 2.
[261] As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, dimethylethanolamine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, Aqueous solutions, such as 1, 5- diazabicyclo- [4.3.0] -5-nonene, are preferable.
[262] A suitable amount of water-soluble organic solvents such as methanol and ethanol, surfactants and the like may be added to the alkaline developer. In addition, after alkali development, it wash | cleans normally with water.
[263] As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (immersion) developing method, and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.
[264] The extraction amount of the caprolactone component by acetonitrile of the colored layer formed from the radiation sensitive composition for color liquid crystal display devices of the present invention is 5% by weight or less, preferably 3% by weight or less of the colored layer.
[265] In the present invention, a color liquid crystal display device which does not cause image baking during operation of the display panel can be obtained by setting the extraction amount of the caprolactone component by the acetonitrile of the colored layer to 5% by weight or less of the colored layer.
[266] The extraction amount measurement of the caprolactone component by acetonitrile of the colored layer of this invention forms a colored layer according to the conditions which form the colored layer for color liquid crystal display devices from the radiation sensitive composition of this invention on a suitable board | substrate, and The test piece of the colored layer was cut out from the substrate, and 100 mg of this test piece was sufficiently mixed with 10 cc of acetonitrile at room temperature, followed by filtration to separate the insoluble component, and the amount of the caprolactone component in the obtained "filtrate" was determined by gas chromatography (elution solvent). : Tetrahydrofuran). In this case, the substrate used is not necessarily the same as the substrate for the color liquid crystal display device, and the mixing conditions such as the shape of the test piece, the mixing method, and the mixing time extract the entire amount of the caprolactone component contained in the test piece by acetonitrile. It does not specifically limit, as long as it can be done.
[267] The color liquid crystal display element which has the pixel and / or black matrix formed from the radiation sensitive composition for color liquid crystal display devices of this invention can be applied to a transmissive and reflective color liquid crystal display device, and also the color liquid crystal display device of this invention. The radiation sensitive composition for this is useful also for a color image tube element, a color sensor, etc. of a thin-film transistor (TFT) system.
[268] Embodiment of the Invention
[269] The radiation sensitive composition for color liquid crystal display devices of this invention contains the said (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator as an essential component, and also formed from this composition. Although the extraction amount of the caprolactone component by the acetonitrile of a colored layer is 5 weight% or less of the said colored layer, Although a preferable composition is concretely illustrated, it is as follows [1]-[9].
[270] [1] A radiation-sensitive composition for color liquid crystal display devices, wherein the total amount (mmol) of the polymerizable unsaturated bond in the polyfunctional monomer (C) is 2 to 4 mmol / g based on the total amount (g) of the components (A) to (D). .
[271] [2] A radiation sensitive composition for a color liquid crystal display device, wherein the colorant (A) is a pigment and further contains a dispersant having a urethane bond.
[272] [3] The radiation sensitive composition for color liquid crystal display device according to the above [1] or [2], wherein the alkali-soluble resin (B) contains a carboxyl group-containing copolymer (I).
[273] [4] The radiation sensitive composition for a color liquid crystal display device according to the above [3], wherein the carboxyl group-containing copolymer (I) is a carboxyl group-containing copolymer (II).
[274] [5] The method according to any one of [1] to [4], wherein (C) the polyfunctional monomer is selected from the group of trimethylolpropanetriacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. The radiation sensitive composition for color liquid crystal display devices which consist of 1 or more types.
[275] [6] The color liquid crystal according to any one of [1] to [5], wherein the photopolymerization initiator (D) comprises at least one member selected from the group of acetophenone compounds, biimidazole compounds, and triazine compounds. Radiation-sensitive composition for display devices.
[276] [7] The radiation sensitive composition for a color liquid crystal display device according to any one of the above [1] to [6], wherein the photopolymerization initiator (D) comprises a biimidazole compound and a hydrogen donor.
[277] [8] The radiation sensitive composition for color liquid crystal display device according to the above [7], wherein the photopolymerization initiator (D) further comprises at least one member selected from the group of acetophenone compounds and triazine compounds.
[278] [9] The amount of extraction of the caprolactone component by acetonitrile of the colored layer formed from the radiation sensitive composition for a color liquid crystal display device according to any one of the above [1] to [8], preferably 3 The radiation sensitive composition for color liquid crystal display devices which is weight% or less.
[279] Moreover, the preferable aspect in the manufacturing method of the colored layer of this invention includes the following process.
[280] (1) Process of forming the coating film of the radiation sensitive composition for color liquid crystal display devices in any one of said [1]-[9] on a TFT system liquid crystal drive substrate.
[281] (2) Process of exposing at least a part of said coating film and then developing.
[282] In addition, a preferred color liquid crystal display device of the present invention has a structure in which a colored layer is formed directly or through a passivation film on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device, wherein the colored layer is the above [1]. It is formed from the radiation sensitive composition for color liquid crystal display devices in any one of [9].
[283] Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.
[284] The measurement and evaluation in an Example and a comparative example were performed as follows.
[285] Determination of the amount of caprolactone component extracted
[286] After the substrate on which the silicon nitride film was formed on the surface of the TFT type liquid crystal driving substrate was coated with each liquid composition using a spin coater on the surface, it was prebaked in a clean oven at 90 ° C. for 10 minutes to form a coating film having a thickness of 5.0 μm. It was.
[287] Subsequently, after cooling this board | substrate to room temperature, the ultraviolet-ray which has each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film with the exposure amount of 5,000 J / m <2> through a photomask using a high pressure mercury lamp, and a colored layer. (Continuous film) was formed. Thereafter, 100 mg of the colored layer was cut out from the substrate to form a test piece. The test piece was mixed with 10 cc of acetonitrile, sonicated for 15 minutes, shaken for another 30 minutes, and left overnight. Thereafter, an ultrasonic wave was further applied for 15 minutes, filtered through a filter having a pore diameter of 1 µm, and the insoluble components were separated by filtration. The filtrate was analyzed by gas chromatography (elution solvent: tetrahydrofuran) to measure the extraction amount of the caprolactone component. It was.
[288] Baking evaluation
[289] LCD:
[290] A nematic liquid crystal (trade name ZLI-5081, manufactured by Merck Japan Co., Ltd.) consisting of a derivative of fluorobiphenyl was used.
[291] Fabrication of Liquid Crystal Display Devices:
[292] (1) After forming a patterned 1 cm 2 ITO film on one surface of the glass substrate, a commercially available liquid crystal aligning agent for an active matrix is coated on the ITO film using a spinner, and then dried at 180 ° C. for 1 hour to form a film. A coating film having a thickness of 600 kPa was formed.
[293] (2) After forming the patterned 1 cm <2> ITO film | membrane on the color filter formed using the liquid composition of each comparative example, it carried out similarly to (1) on this ITO film | membrane, and formed the coating film of the liquid crystal aligning agent.
[294] (3) The patterned 1 cm <2> ITO film | membrane was formed on the color filter formed using the liquid composition of each Example, and the coating film of the liquid crystal aligning agent was formed like this (1) on this ITO film | membrane.
[295] (4) After forming an ITO film (continuous film) on one side of a glass substrate, it carried out similarly to (1) on this ITO film, and formed the coating film of the liquid crystal aligning agent.
[296] (5) Next, the rubbing process was carried out using the rubbing machine provided with the roll which covered the rayon cloth, and the liquid crystal aligning film was formed on the coating film surface on each board | substrate obtained by ①-④. At this time, the rubbing conditions were roll rotation speed 400rpm, stage movement speed 3cm / sec, and the indentation length of the hair 0.4mm.
[297] ⑥ In this way, in the substrate on which the liquid crystal alignment film is formed, each substrate subjected to the treatment of ①, ② or ③ is combined with the substrate subjected to the treatment of ④ to make one set of two sheets, and each substrate has a diameter of 5.5 μm in two substrates. After the epoxy resin adhesive containing the silica gel columnar spacer was applied by screen printing, two substrates were disposed to face each other so that the rubbing direction of each liquid crystal aligning film was crossed by 90 degrees, and the outer edges of each substrate were in contact with each other. It was pressed to cure the adhesive.
[298] (7) Next, after filling and filling nematic liquid crystal "ZLI-5081" in the cell gap partitioned by the inner surface of two board | substrates of each board | substrate, and the hardened layer of an adhesive agent for each group, the injection hole was sealed and the liquid crystal cell was produced. Then, the polarizing plate was affixed on the outer surface of the liquid crystal cell so that the polarization direction might correspond with the rubbing direction of the liquid crystal aligning film on each board | substrate, and the liquid crystal display element was produced.
[299] Evaluation method of baking:
[300] (1) A function generator WAVE FACTRY (manufactured by NF ELECTRONIC. INSTRUMENT) is connected to the liquid crystal display element, and a square wave voltage of AC 3V and DC 1V is applied, and the liquid crystal display element is heated to 70 ° C for 1 hour.
[301] (2) After heating, the liquid crystal display device is cooled for 5 minutes by cutting off the square wave voltage, and then the square wave voltage of 30 kHz and halftone voltage is applied by the function generator.
[302] ③ Flickr R9211C FFT SERVO ANALYZER (ADVANTEST Co., Ltd.) was put into the oscilloscope 54600A OSCILLOSCOPE (manufactured by HEWLETT PACKARD) using the LCD EVALUATLON SYSTEM (manufactured by Photal) to obtain the flicker waveform obtained from the flicker appearance pulse data on the display of the liquid crystal display device. Flicker strength).
[303] (4) An offset voltage is applied by the function generator, and the offset voltage at the point where the flicker waveform is completely removed is measured to be the flicker erase voltage (ie, the bake removal voltage). The baking degree becomes more remarkable as the flicker erase voltage is larger, and baking does not occur when the flicker erase voltage is less than 50 mA, but baking occurs when it is 50 mA or more.
[304] Here, the baking is "good" for the case where the flicker erase voltage is less than 10 kV, and the baking is "good" for the case where the baking is more than 10 kPa or less than 50 kPa.
[305] <Example>
[306] <Example 1>
[307] (Example using a urethane-based dispersant as (B) component)
[308] Preparation of radiation sensitive composition
[309] (A) 80 parts by weight of CI Pigment Green 7 as a pigment, (B) 12 parts by weight of a urethane-based dispersant (trade name Disperbyk-170) as a dispersant, (C) (meth) acrylic acid / succinic acid mono [2- (meth ) Acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer (copolymer weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) 100 parts by weight, (D) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (E) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator , And 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent to prepare a liquid composition (G1) of the radiation-sensitive composition.
[310] Here, the ratio of the total amount (mmol) of the polymerizable unsaturated bonds in the (C) polyfunctional monomer of G1 to the total amount (g) of the components (A) to (D) is calculated as 1.8 (mmol / g).
[311] Formation of Pixel Array
[312] After coating the liquid composition (G1) using a spin coater on the surface of the substrate on which the silicon nitride film was formed on the surface of the TFT type liquid crystal drive substrate, prebaking was performed in a clean oven at 90 ° C. for 10 minutes to apply a film having a thickness of 2 μm. A film was formed.
[313] Subsequently, after cooling the substrate to room temperature, ultraviolet rays having respective wavelengths of 365 nm, 405 nm and 436 nm were exposed to the coating film through a photomask using a high pressure mercury lamp at an exposure amount of 2,00 J / m 2. . Thereafter, the substrate was immersed in a 0.1 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 1 minute to develop, washed with ultrapure water, and air dried. Thereafter, the substrates were postbaked in a clean oven at 220 ° C. for 25 minutes to form a green striped pixel array on the substrate.
[314] evaluation
[315] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not recognized on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[316] In addition, the surface roughness Ra measured at the measurement length of 10 mm using a stylus type surface roughness meter ("Alpha Step 500" manufactured by KLA Tencol Co., Ltd.) was 20 Hz, and the surface of the pixel was observed with an optical microscope. The surface smoothness of the pixel was excellent.
[317] In addition, the amount of extraction of the caprolactone component of the test piece obtained from the liquid composition (G1) was 3% by weight, and the flicker scavenging voltage was 20 kW, and the baking was "good".
[318] <Example 2>
[319] (Example in which a urethane-based dispersant is used as the component (B) and the ratio of the total amount of the polymerizable unsaturated bonds in the component (C) to the total amount of the components (A) to (D) is a predetermined value)
[320] Preparation of radiation sensitive composition
[321] (A) 80 parts by weight of CI Pigment Green 7 as a pigment, (B) 12 parts by weight of a urethane-based dispersant as a dispersant (trade name Disperbyk-170), (C) methacrylic acid / N-phenylmaleimide / benzyl meta as an alkali-soluble resin. Acrylate / glycerol monomethacrylate / styrene copolymer (copolymer weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) 75 parts by weight, (D) dipentaerythritol hexa as polyfunctional monomer 75 parts by weight of acrylate, (E) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent The parts were mixed to prepare a liquid composition (G2) of the radiation sensitive composition.
[322] The ratio of the total amount (mmol) of the polymerizable unsaturated bond in the (C) polyfunctional monomer of G2 to the total amount (g) of the components (A) to (D) is calculated as 2.7 (mmol / g).
[323] Formation of Pixel Array
[324] A green striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (G2) was used.
[325] evaluation
[326] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not recognized on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[327] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 15 Hz, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[328] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (G2) was 1% by weight of the test piece, and the flicker scavenging voltage was 5 kW, so that baking was "excellent".
[329] <Example 3>
[330] (Example in which a urethane-based dispersant is used as the component (B) and the ratio of the total amount of the polymerizable unsaturated bonds in the component (C) to the total amount of the components (A) to (D) is a predetermined value)
[331] Preparation of radiation sensitive composition
[332] (A) 50 parts by weight of carbon black as a pigment, (B) 15 parts by weight of a urethane-based dispersant (trade name Disperbyk-165) as a dispersant, (C) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / as an alkali-soluble resin. 100 parts by weight of glycerol monomethacrylate / styrene copolymer (copolymer weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000), (D) dipentaerythritol hexaacrylate 50 as a polyfunctional monomer. Parts by weight, (E) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent A liquid composition (BK1) of radiation sensitive composition was prepared.
[333] Here, the ratio of the total amount (mmol) of the polymerizable unsaturated bonds in the (C) polyfunctional monomer of BK1 to the total amount (g) of the components (A) to (D) is calculated as 2.0 (mmol / g).
[334] Formation of black matrix
[335] After coating the liquid composition (BK1) using a spin coater on the surface of the substrate on which the silicon nitride film was formed on the surface of the TFT type liquid crystal driving substrate, prebaking was performed in a clean oven at 90 ° C. for 10 minutes to apply a film having a thickness of 5 μm. A film was formed.
[336] Subsequently, after cooling the substrate to room temperature, ultraviolet rays having respective wavelengths of 365 nm, 405 nm and 436 nm were exposed to the coating film through a photomask using a high pressure mercury lamp at an exposure amount of 4,00 J / m 2. Thereafter, the substrate was immersed in a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C. for 1 minute to develop, then washed with ultrapure water and air dried. Thereafter, the substrate was postbaked in a clean oven at 220 ° C. for 25 minutes to form a black matrix having a black pattern formed on the substrate.
[337] evaluation
[338] When the obtained black matrix was observed using the optical microscope, the developing residue was not confirmed on the board | substrate of an unexposed part, and also the adhesiveness of the black matrix with the board | substrate was excellent.
[339] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 22 GPa, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[340] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (BK1) was 2% by weight, and the flicker cancellation voltage was 25 kW, and baking was "good".
[341] <Example 4>
[342] (Example in which a urethane-based dispersant is used as the component (B) and the ratio of the total amount of the polymerizable unsaturated bonds in the component (C) to the total amount of the components (A) to (D) is a predetermined value)
[343] Preparation of radiation sensitive composition
[344] (A) 50 parts by weight of CI pigment black as a pigment, (B) 15 parts by weight of a urethane-based dispersant as a dispersant (trade name Disperbyk-170), (C) methacrylic acid / N-phenylmaleimide / benzyl methacryl as an alkali-soluble resin. Latex / glycerol monomethacrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) 75 parts by weight, (D) dipentaerythritol hexaacrylic as a polyfunctional monomer Rate 75 parts by weight, (E) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent Mixing to prepare a liquid composition (BK2) of the radiation sensitive composition.
[345] Here, the ratio of the total amount (mmol) of the polymerizable unsaturated bond in the (C) polyfunctional monomer of BK2 to the total amount (g) of the components (A) to (D) is calculated as 2.9 (mmol / g).
[346] Formation of black matrix
[347] A black matrix was formed on the substrate in the same manner as in Example 3 except that the liquid composition (BK2) was used.
[348] evaluation
[349] When the obtained black matrix was observed using the optical microscope, developing residue was not confirmed on the board | substrate of an unexposed part, and also the adhesiveness of the black matrix with the board | substrate was excellent.
[350] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 19 Hz, and when the surface of the pixel was observed with an optical microscope, surface roughness was not confirmed, and the surface smoothness of the pixel was excellent.
[351] In addition, the amount of extraction of the caprolactone component of the test piece obtained from the liquid composition (BK2) was 2% by weight, and the flicker erase voltage was 8 kW, which resulted in "excellent" baking.
[352] Example 5
[353] (Example in which the total amount of the polymerizable unsaturated bonds in the component (C) accounts for the total amount of the components (A) to (D) as a predetermined value)
[354] Preparation of radiation sensitive composition
[355] (A) 80 parts by weight of carbon black as a pigment, (B) 12 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) (meth) acrylic acid / succinic acid mono [2- (meth) acrylic as an alkali-soluble resin Iloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) 60 parts by weight, (D) 90 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (E) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and a solvent As a mixture, 1,000 parts by weight of propylene glycol monomethyl ether acetate was mixed to prepare a liquid composition (BK3) of the radiation sensitive composition.
[356] Here, the ratio of the total amount (mmol) of the polymerizable unsaturated bonds in the (C) polyfunctional monomer of BK3 to the total amount (g) of the components (A) to (D) is calculated as 3.2 (mmol / g).
[357] Formation of black matrix
[358] A black matrix was formed on the substrate in the same manner as in Example 3 except that the liquid composition (BK3) was used.
[359] evaluation
[360] When the obtained black matrix was observed using the optical microscope, developing residue was not confirmed on the board | substrate of an unexposed part, and also the adhesiveness of the black matrix with the board | substrate was excellent.
[361] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 12 GPa, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[362] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (BK3) was 3% by weight, and the flicker cancellation voltage was 24 kV, and baking was "good".
[363] <Example 6>
[364] (Example in which the total amount of the polymerizable unsaturated bonds in the component (C) accounts for the total amount of the components (A) to (D) as a predetermined value)
[365] Preparation of radiation sensitive composition
[366] (A) 50 parts by weight of carbon black as a pigment, (B) 15 parts by weight of a polyethyleneimine dispersant as a dispersant (trade name Solsperse24000), (C) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / as an alkali-soluble resin. Glycerol monomethacrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) 60 parts by weight, (D) dipentaerythritol hexaacrylate 90 as polyfunctional monomer Parts by weight, (E) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent A liquid composition (BK4) of radiation sensitive composition was prepared.
[367] The ratio of the total amount (mmol) of the polymerizable unsaturated bond in the (C) polyfunctional monomer of BK4 to the total amount (g) of the components (A) to (D) is calculated as 3.5 (mmol / g).
[368] Formation of black matrix
[369] A black matrix was formed on the substrate in the same manner as in Example 3 except that the liquid composition (BK4) was used.
[370] evaluation
[371] When the obtained black matrix was observed using the optical microscope, developing residue was not confirmed on the board | substrate of an unexposed part, and also the adhesiveness of the black matrix with the board | substrate was excellent.
[372] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 14 Hz, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[373] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (BK4) was 2% by weight, and the flicker scavenging voltage was 28 kW, indicating that baking was "good".
[374] <Example 7>
[375] (Example in which the total amount of the polymerizable unsaturated bonds in the component (C) accounts for the total amount of the components (A) to (D) as a predetermined value)
[376] Preparation of radiation sensitive composition
[377] (A) 100 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Red 177 and CI Pigment Red 224 as a colorant, (B) 10 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) alkali-soluble Methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer (copolymer weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) as resin Parts, (D) 80 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (E) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 50 as the photopolymerization initiator By weight and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (R1) of the radiation sensitive composition.
[378] The ratio of the total amount (mmol) of the polymerizable unsaturated bonds in the (C) polyfunctional monomer of R1 to the total amount (g) of the components (A) to (D) is calculated as 2.7 (mmol / g).
[379] Formation of Pixel Array
[380] A red striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (R1) was used.
[381] evaluation
[382] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not confirmed on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[383] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 25 GPa, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[384] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (R1) was 1% by weight of the test piece, and the flicker scavenging voltage was 7 kW, so that baking was "good".
[385] <Example 8>
[386] (Example in which the total amount of the polymerizable unsaturated bonds in the component (C) accounts for the total amount of the components (A) to (D) as a predetermined value)
[387] Preparation of radiation sensitive composition
[388] (A) 100 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Red 177 and CI Pigment Red 224 as a colorant, (B) 10 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) alkali-soluble Methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer (copolymer weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) as resin Part, (D) 80 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (E) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanoone- as the photopolymerization initiator- 1 20 parts by weight, 15 parts by weight of 4,4'-bis (diethylamino) benzophenone as a sensitizer and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to form a liquid composition (R2) of the radiation-sensitive composition. Prepared.
[389] The ratio of the total amount (mmol) of the polymerizable unsaturated bond in the (C) polyfunctional monomer of R2 to the total amount (g) of the components (A) to (D) is calculated as 2.9 (mmol / g).
[390] Formation of Pixel Array
[391] A red striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (R2) was used.
[392] evaluation
[393] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not confirmed on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[394] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 30 Hz, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[395] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (R2) was 1% by weight of the test piece, and the flicker scavenging voltage was 5 kW, and baking was "excellent".
[396] Example 9
[397] (Example in which the total amount of the polymerizable unsaturated bonds in the component (C) accounts for the total amount of the components (A) to (D) as a predetermined value)
[398] Preparation of radiation sensitive composition
[399] (A) 55 parts by weight of a 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, (B) 10 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) Methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer weight ratio = 15/15/70, Mw = 25,000, Mn = 10,000) as alkali-soluble resin 75 weight part, (D) polyfunctionality 75 parts by weight of dipentaerythritol hexaacrylate as a monomer, (E) 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- as a photopolymerization initiator. 6 parts by weight of biimidazole, 6 parts by weight of 4,4'-bis (diethylamino) benzophenone as an amine hydrogen donor, 3 parts by weight of 2-mercaptobenzothiazole as mercaptan-based hydrogen donor, and propylene glycol as a solvent Liquid composition of the radiation sensitive composition by mixing 700 parts by weight of monomethyl ether acetate and 300 parts by weight of cyclohexane A (B1) was prepared.
[400] The ratio of the total amount (mmol) of the polymerizable unsaturated bond in the (C) polyfunctional monomer of B1 to the total amount (g) of the components (A) to (D) is calculated as 3.5 (mmol / g).
[401] Formation of Pixel Array
[402] A blue striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (B1) was used.
[403] evaluation
[404] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not confirmed on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[405] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 30 Hz, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[406] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (B1) was 1% by weight of the test piece, and the flicker scavenging voltage was 3 kW, so that baking was "excellent".
[407] <Example 10>
[408] (Example in which the total amount of the polymerizable unsaturated bonds in the component (C) accounts for the total amount of the components (A) to (D) as a predetermined value)
[409] Preparation of radiation sensitive composition
[410] (A) 100 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 150 as a colorant, (B) 10 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) alkali solubility 75 parts by weight of methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer weight ratio = 15/15/70, Mw = 25,000, Mn = 10,000) as the resin, (D) as a polyfunctional monomer Radiation-sensitive by mixing 75 parts by weight of dipentaerythritol hexaacrylate, (E) 10 parts by weight of a triazine compound (3) as a photopolymerization initiator, and 700 parts by weight of propylene glycol monomethyl ether acetate as a solvent and 300 parts by weight of cyclohexane A liquid composition (G3) of the composition was prepared.
[411] Here, the ratio of the total amount (mmol) of the polymerizable unsaturated bonds in the (C) polyfunctional monomer of G3 to the total amount (g) of the components (A) to (D) is calculated as 3.0 (mmol / g).
[412] Formation of Pixel Array
[413] A green striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (G3) was used.
[414] evaluation
[415] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not confirmed on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[416] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 30 Hz, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[417] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (G2) was 1% by weight of the test piece, and the flicker scavenging voltage was 5 kW, so that baking was "excellent".
[418] Comparative Example 1
[419] (Example of not using a urethane type dispersing agent as (B) component and making the ratio which the total amount of the polymerizable unsaturated bond in (C) component occupy in the total amount of (A)-(D) component; the same below)
[420] Preparation of radiation sensitive composition
[421] (A) 80 parts by weight of CI Pigment Green 7 as a pigment, (B) 12 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) (meth) acrylic acid / succinic acid mono [2- (meth ) Acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer (copolymer weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) 100 parts by weight, (D) 50 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (E) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator. Part and a 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (g1) of the radiation sensitive composition.
[422] Formation of Pixel Array
[423] A green striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (g1) was used.
[424] evaluation
[425] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not confirmed on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[426] However, the surface roughness Ra measured in the same manner as in Example 1 was 40 GPa, and when the surface of the pixel was observed under an optical microscope, the surface roughness was confirmed.
[427] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (g1) was 9% by weight of the test piece, and the flicker scavenging voltage was 80 kV.
[428] Comparative Example 2
[429] Preparation of radiation sensitive composition
[430] (A) 50 parts by weight of carbon black as a pigment and 15 parts by weight of barium sulfate, (B) 15 parts by weight of polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) (meth) acrylic acid / succinic acid mono [2] as alkali-soluble resin. -(Meth) acryloyloxyethyl] / N-phenylmaleimide / benzyl (meth) acrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) 100 Parts by weight, (D) 50 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (E) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as the photopolymerization initiator 50 parts by weight, and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (bk1) of the radiation sensitive composition.
[431] Formation of Pixel Array
[432] A black matrix was formed on a substrate in the same manner as in Example 3 except that the liquid composition (bk1) was used.
[433] evaluation
[434] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not confirmed on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[435] However, the surface roughness Ra measured in the same manner as in Example 1 was 50 Hz, and the surface of the pixel was observed under an optical microscope.
[436] In addition, the extraction amount of the caprolactone component of the test piece obtained from the liquid composition (bk1) was 7% by weight of the test piece, and the flicker scavenging voltage was 60 mA, which resulted in "bad" baking.
[437] Comparative Example 3
[438] Preparation of radiation sensitive composition
[439] (A) 100 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Red 177 and CI Pigment Red 224 as a colorant, (B) 10 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) alkali-soluble Methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer (copolymer weight ratio = 15/25/35/10/15, Mw = 30,000, Mn = 10,000) as resin Parts, (D) 120 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (E) 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- as a photoinitiator 1 20 parts by weight of 4,4'-bis (diethylamino) benzophenone as a sensitizer and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (r1) of the radiation-sensitive composition. Prepared.
[440] Here, the ratio of the total amount (mmol) of the polymerizable unsaturated bonds in the (C) polyfunctional monomer of r1 to the total amount (g) of the components (A) to (D) is calculated as 4.4 (mmol / g).
[441] Formation of Pixel Array
[442] A red striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (r1) was used.
[443] evaluation
[444] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, the developing residue was not confirmed on the board | substrate of an unexposed part, and the adhesiveness of the pixel with the board | substrate was also excellent.
[445] In addition, the surface roughness Ra measured in the same manner as in Example 1 was 20 Hz, and when the surface of the pixel was observed with an optical microscope, the surface roughness was not confirmed and the surface smoothness of the pixel was excellent.
[446] However, when the cross-sectional shape of the pattern was observed by SEM, it was inversely tapered.
[447] The extraction amount of the caprolactone component of the test piece obtained from the liquid composition (r1) was 6% by weight of the test piece, and the flicker scavenging voltage was 52 kW, resulting in "bad" baking. In addition, the occurrence of the marking unevenness was observed at this time.
[448] <Comparative Example 4>
[449] Preparation of radiation sensitive composition
[450] (A) 55 parts by weight of a 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a coloring agent, (B) 10 parts by weight of a polyethyleneimine dispersant (trade name Solsperse24000) as a dispersant, (C) Methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymer weight ratio = 15/15/70, Mw = 25,000, Mn = 10,000) as alkali-soluble resin 110 parts by weight, (D) polyfunctional 40 parts by weight of dipentaerythritol hexaacrylate as a monomer, (E) 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- as a photopolymerization initiator. 6 parts by weight of biimidazole, 6 parts by weight of 4,4'-bis (diethylamino) benzophenone as an amine hydrogen donor, 3 parts by weight of 2-mercaptobenzothiazole as mercaptan-based hydrogen donor, and propylene glycol as a solvent Mixing 700 parts by weight of monomethyl ether acetate and 300 parts by weight of cyclohexanone to form a liquid bath of the radiation-sensitive composition Product (b1) was prepared.
[451] Here, the ratio of the total amount (mmol) of the polymerizable unsaturated bonds in the (C) polyfunctional monomer of b1 to the total amount (g) of the components (A) to (D) is calculated as 1.9 (mmol / g).
[452] Formation of Pixel Array
[453] A blue striped pixel array was formed on a substrate in the same manner as in Example 1 except that the liquid composition (b1) was used.
[454] evaluation
[455] When the obtained pixel array was observed using the optical microscope, the through-hole of 5 micrometer angle was also opened, and the developing residue was not confirmed on the board | substrate of an unexposed part.
[456] However, the adhesion of the pixel to the substrate is difficult, and pattern peeling occurs in part.
[457] The surface roughness Ra measured in the same manner as in Example 1 was 60 Hz, and when the surface of the pixel was observed with an optical microscope, the surface roughness was confirmed and the surface smoothness of the pixel was inferior.
[458] The amount of extraction of the caprolactone component of the test piece obtained from the liquid composition (r1) was 8% by weight of the test piece, and the flicker scavenging voltage was 65 kW, resulting in "bad" baking. In addition, the occurrence of the marking unevenness was observed at this time.
[459] According to the present invention, it is possible to form a conductive path of 5 μm or less, to form a forward tapered pixel, and to prevent development residue during development, without causing an image to be baked during operation of the display panel. And a color used for forming a colored layer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device having excellent adhesion to a driving substrate including a thin film transistor (TFT) and a passivation film such as a silicon nitride film. There is provided a radiation-sensitive composition for a liquid crystal display device, a method of forming a colored layer therefrom, a colored layer formed thereby, and a color liquid crystal display device having the colored layer.

权利要求:
Claims (10)
[1" claim-type="Currently amended] A radiation sensitive composition for color liquid crystal displays containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, capro by acetonitrile of the colored layer formed from this composition The radiation sensitive composition for color liquid crystal display devices used for forming a colored layer on the board | substrate for a drive of a thin film transistor (TFT) system color liquid crystal display device whose extraction amount of a lactone component is 5 weight% or less of this colored layer.
[2" claim-type="Currently amended] The radiation sensitive composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, Comprising: (C) Polymerizable unsaturated bond in a polyfunctional monomer The radiation-sensitive composition for color liquid crystal display devices whose total amount (mmol) is 2-4 mmol / g with respect to the total amount (g) of (A)-(D) component.
[3" claim-type="Currently amended] The radiation sensitive composition for color liquid crystal display devices of Claim 1 whose (A) coloring agent is a pigment and also contains the dispersing agent which has a urethane bond.
[4" claim-type="Currently amended] The color liquid crystal display device according to any one of claims 1 to 3, wherein (D) the photopolymerization initiator comprises at least one selected from the group consisting of acetophenone compounds, biimidazole compounds, and triazine compounds. Radiation-sensitive composition for use.
[5" claim-type="Currently amended] The radiation sensitive composition for color liquid crystal display devices as described in any one of Claims 1-3 in which (D) photoinitiator contains a biimidazole type compound and a hydrogen donor.
[6" claim-type="Currently amended] The radiation sensitive composition for color liquid crystal display devices of Claim 5 which (D) photoinitiator further contains 1 or more types chosen from the group of an acetophenone type compound and a triazine type compound.
[7" claim-type="Currently amended] (B) Alkali-soluble resin is mono (meth) in any one of (a) 1 or more types of polymerizable unsaturated monomers which have one or more carboxyl groups, and (b) polymer molecular chain ends. 1) at least one selected from the group consisting of macromonomers having acryloyl group, N-position substituted maleimides, 2-hydroxy (meth) acrylate, benzyl (meth) acrylate and glycerol mono (meth) acrylate The radiation sensitive composition for color liquid crystal display devices containing a copolymer with.
[8" claim-type="Currently amended] (1) Process of forming the coating film of the radiation sensitive composition for color liquid crystal display devices of any one of Claims 1-3 on the thin film transistor (TFT) system liquid crystal drive board | substrate,
(2) The manufacturing method of a colored layer including the process of exposing at least one part of the said coating film, and then developing.
[9" claim-type="Currently amended] The colored layer for color liquid crystal display devices formed from the radiation sensitive composition for color liquid crystal display devices of any one of Claims 1-3.
[10" claim-type="Currently amended] The color liquid crystal display element formed by forming the colored layer for color liquid crystal display devices of Claim 9 on the drive board | substrate of a thin film transistor (TFT) system color liquid crystal display device.

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同族专利:

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公开号 | 公开日

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TWI242079B|2005-10-21|

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JP2002040225A|2002-02-06|

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:
2000-07-27|Priority to JPJP-P-2000-00226462

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2000-07-27|Priority to JP2000226462A

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2001-07-26|Application filed by 마쯔모또 에이찌, 제이에스알 가부시끼가이샤

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2002-02-02|Publication of KR20020010085A

优先权:

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申请号 | 申请日 | 专利标题

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JPJP-P-2000-00226462|2000-07-27|

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JP2000226462A|JP2002040225A|2000-07-27|2000-07-27|Radiation sensitive composition for color liquid crystal display device and color liquid crystal display device|