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    • 专利摘要:
    Oligomers or polymers (A) containing at least one carboxylic acid group in a molecule and having a molecular weight of 200,000 or less, At least one photoinitiator compound of formula (B) and Photosensitive compositions comprising monomeric, oligomeric or polymeric compounds (C) having at least one olefinic double bond are particularly suitable for preparing photoresists, in particular color filters. Formula I In Formula I above, R 1 is straight or branched C 1 -C 12 alkyl, R 2 is straight or branched C 1 -C 4 alkyl, R 3 and R 4 independently of one another are straight or branched C 1 -C 8 alkyl.
    公开号:KR20040030848A
    申请号:KR10-2004-7001011
    申请日:2002-07-18
    公开日:2004-04-09
    发明作者:구라히사토시；오카히데타카；오와마사키
    申请人:시바 스페셜티 케미칼스 홀딩 인크.；
    IPC主号:
    专利说明:

    Photosensitive resin composition
    [1] The present invention relates to a photosensitive composition which can be developed by an alkaline solution, comprising a selected α-aminoalkylphenone compound as a photoinitiator.
    [2] From US Pat. No. 5,077,402, α-aminoalkylphenones are known as photoinitiators. Japanese Patent Publication No. 2678684 B2 describes a color filter resist composition comprising 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one. International Publication Nos. WO 98/00759 A1 and WO 0068740 A1 describe alkali developable solder compositions comprising photoinitiators. Similar alkali developable compositions for the manufacture of plasma display panels are described in Japanese Patent Laid-Open Nos. 11306964 A2, 11149862 A2, 11072909 A2, and 11065102 A2.
    [3] In photopolymerization technology, it is excellent in reactivity, alkali developable, easy to handle, exhibits excellent developability, and meets high industrial requirements for properties such as, for example, thermal stability and storage stability. There is still a need for a composition that is particularly suitable as an imaging formulation.
    [4] Surprisingly, oligomers or polymers (A) containing at least one carboxylic acid group in a molecule and having a molecular weight of 200,000 or less,
    [5] At least one photoinitiator of formula (B) and
    [6] It has been found that photosensitive compositions comprising monomeric, oligomeric or polymeric compounds (C) having at least one olefinic double bond unexpectedly exhibit excellent performance.
    [7]
    [8] In Formula I above,
    [9] R 1 is straight or branched C 1 -C 12 alkyl,
    [10] R 2 is straight or branched C 1 -C 4 alkyl,
    [11] R 3 and R 4 independently of one another are straight or branched C 1 -C 8 alkyl.
    [12] Component (A) in the composition according to the invention is an oligomer or polymer containing at least one free carboxylic acid group in the molecule and having a molecular weight of 200,000 or less.
    [13] Examples of suitable components (A) are polymers (binders) having a molecular weight of about 2,000 to 200,000, preferably 2,000 to 150,000, 2,000 to 100,000 or 5,000 to 100,000. Examples of alkali developable binders are acrylic polymers having carboxylic acid functional groups as pendant groups, for example ethylenically unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylic acid, 2-carboxypropyl (meth ) Acrylic acid, itaconic acid, crotonic acid, maleic acid, maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monopropyl ester, maleic acid monobutyl ester, maleic acid monobenzyl ester, maleic acid mono (2-ethylhexyl ) Esters, maleic acid monohydroxyethyl ester, maleic acid monohydroxypropyl, fumaric acid, fumaric acid monomethyl ester, fumaric acid monoethyl ester, fumaric acid monopropyl ester, fumaric acid monobutyl ester, fumaric acid monobenzyl ester, fumaric acid mono (2- Ethylhexyl) ester, fumaric acid monohydroxyethyl ester, fumaric acid Nohydroxypropyl and ω-carboxypolycaprolactone mono (meth) acrylate] and esters of (meth) acrylic acid [eg methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate , Tricyclo [5.2.1.0 2,6 ] decane-8-yl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl ( Meth) acrylate and 6,7-epoxyheptyl (meth) acrylate], esters of maleic acid and fumaric acid such as maleic dimethyl ester, maleic diethyl ester, maleic dipropyl ester, maleic dibutyl ester, Maleic acid dibenzyl ester, Maleic acid di (2-ethylhexyl) ester, maleic acid dihydroxyethyl ester, maleic acid dihydroxypropyl, fumaric acid dimethyl ester, fumaric acid diethyl ester, fumaric acid dipropyl ester, fumaric acid dibutyl ester, fumaric acid dibenzyl ester, Fumaric acid di (2-ethylhexyl) ester, fumaric acid dihydroxyethyl ester and fumaric acid dihydroxypropyl], vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, vinyl benzyl glycidyl Ether], amide unsaturated compounds [e.g. (meth) acrylamide, diacetone acrylamide, N-methylol acrylamide, N-butoxy methacrylamide] and polyolefin compounds [e.g. butadiene, isoprene, chloroprene, etc.] At least one monomer selected from mono-2-[(meth) acryloyloxy] ethyl succinate, N-phenylmaleimide, male Commonly known obtained by copolymerization with anhydride, methacrylonitrile, methyl isopropenyl ketone, vinyl acetate, vinyl propionate, vinyl pivalate, polystyrene macromonomer or polymethyl (meth) acrylate macromonomer Is a copolymer. Examples of copolymers include copolymers of acrylates and methacrylates with acrylic acid or methacrylic acid or with styrene or substituted styrenes, copolymers with phenolic resins such as novolacs, (poly) hydroxystyrenes, and hydroxy Copolymers of styrene with alkyl acrylates, acrylic acid and / or methacrylic acid. Preferred examples of the copolymer include copolymers of methyl methacrylate / methacrylic acid, copolymers of benzyl methacrylate / methacrylic acid, copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, benzyl methacrylate Copolymer of / methacrylic acid / styrene, copolymer of benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate, copolymer of methyl methacrylate / butyl methacrylate / methacrylic acid / styrene, methyl meta Copolymer of methacrylate / benzyl methacrylate / methacrylic acid / hydroxyphenyl methacrylate, copolymer of methacrylic acid / styrene / benzyl methacrylate / glycerol monomethacrylate / N-phenylmaleimide, methacryl Copolymer of acid / ω-carboxypolycaprolactone monoacrylate / styrene / benzyl / methacrylate / glycerol monomethacrylate / N-phenylmaleimide.
    [14] The polyimide binder resin in the present invention may be a polyimide precursor, for example a poly (amic acid ester) compound optionally having a photopolymerizable side chain group bonded to the main chain or to an ester group in the molecule, or, for example, preferably May be a poly (amic acid), for example aminoacrylate or aminomethacrylate, in which an acrylate or methacrylate having at least one basic group in the molecule is added in solution.
    [15] Further examples for component (A) are oligomers or polymers obtained by the reaction of saturated or unsaturated polybasic acid anhydrides with the reaction products of epoxy compounds with unsaturated monocarboxylic acids. Most advantageous as the epoxy compound used in the preparation are novolac epoxy and bisphenol crab epoxy.
    [16] The resin curable by activating energy may be obtained by reacting the reaction product of a novolak-based epoxy compound (described below) with an unsaturated monocarboxylic acid, such as a dibasic acid anhydride (e.g. phthalic anhydride) or an aromatic polycarboxylic anhydride (e.g. trimellitic anhydride). Or pyromellitic anhydride). In this case, the resin proved to be particularly suitable when the amount of said acid anhydride used in the reaction in its preparation exceeds 0.15 mol per each hydroxyl group included in the reaction product of the novolak-based epoxy compound with the unsaturated carboxylic acid. do.
    [17] The acid value of the resin thus obtained (which is expressed as the number of mg of potassium hydroxide required to neutralize 1 g of resin) is suitably 45 to 160 mg KOH / g, preferably 50 to 140 mg KOH / g. to be.
    [18] When the number of ethylenically unsaturated bonds which exist in the molecular unit of resin curable by an activation energy ray is small, photocuring advances slowly and it is preferable to use a novolak-type epoxy compound as a raw material.
    [19] The novolac epoxy compound is represented by a phenol novolac epoxy resin and a cresol novolac epoxy resin. Compounds produced by reacting epichlorohydrin with a suitable novolak resin in a conventional manner can be used.
    [20] The resins may also be polycarboxylic anhydrides (e.g. benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, trimellitic anhydride) and / or dibasic anhydrides and bisphenol epoxy compounds (e.g. bisphenol fluorene epoxy resins or bisphenol A Epoxy resin) and the reaction product of unsaturated monocarboxylic acid. Typical examples of the photopolymerizable bisphenol-based compound include JP 6-1938-A, JP 7-64281-A, JP 9-241339-A, and JP 9-241339-A. JP 9-304929 and JP 10-3012276. In order to reduce the viscosity of an ink, a bisphenol-A epoxy compound can be used.
    [21] Typical examples of these acid anhydrides are dibasic acid anhydrides (e.g. maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetra Hydrophthalic anhydride, methyl-endomethylenetetrahydrophthalic anhydride, chloric anhydride and methyltetrahydrophthalic anhydride), aromatic polycarboxylic anhydrides such as trimellitic anhydride, pyromellitic anhydride and benzophenone-tetracarboxylic dianhydride, Biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, diphenylsulfontetracarboxylic dianhydride, hexafluoroisopropylidenediphthalic anhydride) and polycarboxylic anhydride derivatives such as 5- (2,5-dioxo Tetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Is water.
    [22] Further examples for component (A) are obtained by adding an epoxy group containing acrylic ester or methacrylic ester compound to a portion of the carboxylic acid group of the copolymer to cause the reaction of acrylate or methacrylate with acrylic acid or methacrylic acid. Reaction product.
    [23] Copolymers of acrylic esters and / or methacrylic esters and acrylic acid and / or methacrylic acid are obtained by copolymerizing one, two or more acrylic esters and / or methacrylic acid. Suitable esters are compounds of formula 1 and suitable acrylic acid and / or methacrylic acid are compounds of formula 2.
    [24]
    [25] In Formula 1 above,
    [26] R a is a hydrogen atom or a methyl group,
    [27] R b is an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
    [28]
    [29] In Formula 2 above,
    [30] R a is as defined above.
    [31] The copolymerization is carried out according to conventional methods, for example solution polymerization.
    [32] Preferably, the molar ratio between acrylic ester and / or methacrylic ester and acrylic acid and / or methacrylic acid is 30:70 to 70:30.
    [33] The ester group of each of the acrylic ester and / or methacrylic acid ester may suitably be selected from various aliphatic groups having 1 to 6 carbon atoms.
    [34] The reaction product is obtained by adding an acrylic ester and / or methacrylic ester having a terminal epoxy group to the copolymer thus obtained and is a compound of formula (3).
    [35]
    [36] In Formula 3 above,
    [37] R a is as defined above,
    [38] R c is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 12 carbon atoms.
    [39] In order to obtain a reaction product suitable for the present invention, the compound of formula 3 is added to the monomer of formula 1 and formula 2 at a rate of 10 to 40 mol% to provide an ultraviolet curable copolymer.
    [40] The reaction product thus obtained preferably has an average molecular weight in the range of 20,000 to 70,000 and a softening point in the range of preferably 35 to 130 ° C and an acid value of 50 to 150.
    [41] Further examples of component (A) are resins having an α, β-unsaturated double bond in the side chain and an acid value of 50 to 200. The photopolymerizable resin is composed of, for example, 70 to 95% by weight of an ethylenically unsaturated acid component and a copolymerizable component thereof. It has an acid value of at least 500, preferably at least 600, in particular at least 620, and having a number average molecular weight of 1,000 to 100,000, preferably of 3,000 to 70,000, a carboxyl group-containing resin, an unsaturated having an α, β-unsaturated double bond and an epoxy group. Addition product formed between compounds. The content of the ethylenically unsaturated acid component in the carboxyl group-containing resin of the photopolymerizable resin is 70 to 95% by weight, so that the photopolymerizable resin (A) is added with an unsaturated compound having an α, β-unsaturated double bond and an epoxy group thereto. It is not insoluble in water or dilute aqueous alkali solution afterwards and remains soluble. Examples of such resins are described in JP 8-339081-A.
    [42] The carboxyl group-containing resin (A) is, for example, 70 to 95% by weight, preferably 78 to 88% by weight, in particular 80 to 85% by weight and 5 to 30% by weight of the copolymer monomer, preferably ethylenically unsaturated acid monomer. Preferably it is produced by dissolving 22-12% by weight, in particular 15-20% by weight, in a suitable non-reactive solvent and thermally polymerizing the solution at 45-120 ° C. in the presence of a thermal polymerization initiator. Therefore, the carboxyl group-containing resin having an acid value of 500 or more and a number average molecular weight of 1,000 to 100,000 can be produced with high purity and high stability.
    [43] Specific examples of ethylenically unsaturated monomers suitable for the preparation of the carboxyl group-containing resin (A) include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3- Isopropyl acrylic acid, succinic acid mono-hydroxyethyl acrylate, phthalic acid mono-hydroxyethyl acrylate, dihydrophthalic acid mono-hydroxyethyl acrylate, tetrahydrophthalic acid mono-hydroxy ethyl acrylate, hexahydrophthalic acid monohydrate Oxyethyl-acrylates, acrylic acid dimers, acrylic acid trimers, ω-carboxy-polycaprolactone monoacrylates and ω-carboxy-polycaprolactone monomethacrylates. Among these monomers, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3-isopropylacrylic acid, ω-carboxy-polycaprolactone monoacrylic And ω-carboxy-poly-caprolactone monomethacrylate and the like, and acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, angelic acid, tiglic acid, 2-ethylacrylic acid, 3-propylacrylic acid, 3 Particular preference is given to isopropylacrylic acid, ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate. These monomers may be used alone or in a mixture of two or more.
    [44] Suitable copolymerizable monomers are acrylic esters, methacrylic esters, vinyl monomers, styrenic monomers and cyclic ester monomers. Specific examples thereof include 2-hydroxymethyl acrylate, 2-hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy Oxypropyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol monoethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, di Pentaerythritol pentamethacrylate, dipentaerythritol pentaacrylate, dimethylaminoethyl acrylate, dimethylamino-ethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydro-furfuryl methacrylate, acrylic acid amide, meta Krylic acid amide, arc Ronitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl-methacrylate, benzyl acrylate, benzyl methacrylate, acrylate carbitol, methacrylate carbitol, ω-caprolactone-modified tetrafurfuryl acrylate, ω-caprolactone Modified tetrafurfuryl methacrylate, diethylene glycol ethoxyl acrylate, isodecyl acrylate, isodecyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, tri Decyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate and the like. These monomers may be used alone or in a mixture of two or more.
    [45] Suitable thermal polymerization initiators are, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile) (usable temperature 45-70 ° C), 2,2'-azobis (isobutyronitrile) (Usable temperature 60-90 ° C), 2,2'-azobis (2-methylisobutyronitrile) (usable temperature 60-95 ° C), tert-butylperoctoate (usable temperature 75-100 ° C), 1,1'-azobis (cyclohexane-1-carbonitrile) (usable temperature 80-110 ° C) or 1-[(1-diazo-1-methylethyl) azo] -formamide (use Possible temperature 95-120 ° C.). In general, for example, one or more of the mentioned compounds are used.
    [46] The carboxyl group-containing resin produced according to the above method is then esterified using an unsaturated compound having an α, β-unsaturated double bond and an epoxy group, whereby the carboxyl group is esterified and the side chain has an α, β-unsaturated double bond. Modified with a photopolymerizable resin. Examples of suitable compounds having α, β-unsaturated double bonds and epoxy groups are provided below. For example, one or more members selected from the group consisting of glycidyl acrylate, glycidyl methacrylate and compounds of formulas 4, 5 and 6 as defined below are used.
    [47]
    [48]
    [49] In Formula 5 above,
    [50] R 1 ′ is hydrogen or methyl,
    [51] n 'is an integer of 1-10.
    [52]
    [53] In Formula 6 above,
    [54] R 2 ′ is hydrogen or methyl,
    [55] n "is an integer of 1-3.
    [56] Among these compounds, compounds having an alicyclic epoxy group are particularly preferable because these compounds have high reactivity with the carboxyl group-containing resin, so that the reaction time can be shortened. These compounds also do not cause gelation during the reaction process so that the reaction can be stably performed. Glycidyl acrylate and glycidyl methacrylate, on the other hand, are advantageous in terms of sensitivity and heat resistance, because they are low molecular weight and can provide a high conversion of esterification.
    [57] The photopolymerizable resin obtained by the above method has an α, β-unsaturated double bond in its side chain. Its acid value is 50 to 200, preferably 70 to 150, in particular 85 to 120. Its number average molecular weight is 7,000 to 10,000 and its glass transition point (hereinafter referred to as Tg) is 30 to 120 ° C. When the photopolymerizable resin is used as the solder resist, the acid value is preferably 70 or more because other additive components may be further added to the composition.
    [58] An inert organic solvent is used when esterifying and preparing the photosensitive resin composition.
    [59] Commercially available unsaturated compounds (A) described above are, for example, EB3800, EB9692, EB9694, EB9695, EB9696 (UCB Chemicals), KAYARAD TCR1025 (Nippon Kayaku Co., LTD.), NEOPOL8319 (U-Pica), EA- 6340 (Shin Nakamura Chemical Co., Ltd.), ACA200M, ACA250 (Daicel Industries, Ltd.).
    [60] The oligomers or polymers (A) are obtained by reacting a binder polymer, in particular a copolymer of (meth) acrylate with (meth) acrylic acid, or a reaction product of a saturated or unsaturated polybasic acid anhydride with an epoxy compound and an unsaturated monocarboxylic acid. Or an addition product formed between an unsaturated compound having an α, β-unsaturated double bond and an epoxy group and a carboxyl group-containing resin.
    [61] The photosensitive composition of the present invention comprises at least one photoinitiator (B) of formula (I).
    [62] C 1 -C 12 alkyl is straight or branched, for example C 1 -C 10 -alkyl, C 1 -C 8 -alkyl, C 1 -C 6 -alkyl, C 1 -C 4 -alkyl, C 6 -C 10 -alkyl, C 8 -C 10 -alkyl, C 6 -C 8 -alkyl, C 4 -C 8 -alkyl or C 4 -C 10 -alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, Nonyl, decyl and dodecyl.
    [63] R 1 is for example straight or branched C 1 -C 4 alkyl, in particular methyl, ethyl, isopropyl, npropyl, isobutyl and n-butyl, and R 2 is for example methyl, ethyl or propyl, especially ethyl , R 3 and R 4 are especially independently of one another straight or branched C 1 -C 4 alkyl, in particular methyl.
    [64] Preferred compounds of formula (I)
    [65] (One)
    [66] 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-isopropylbenzyl) -butan-1-one
    [67] (2)
    [68] 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-methylbenzyl) -butan-1-one
    [69] (3)
    [70] 1- [4-morpholinophenyl] -2-dimethylamino-2- [4- (2-methylprop-1-yl) -benzyl] -butan-1-one
    [71] (4)
    [72] 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-ethylbenzyl) -butan-1-one
    [73] (5)
    [74] 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-n-propylbenzyl) -butan-1-one
    [75] (6)
    [76] 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-n-butylbenzyl) -butan-1-one
    [77] These photoinitiators are known. Its preparation is described, for example, in US Pat. No. 5,077,402 (col. 16 ff.).
    [78] Suitable amounts of component (B) are 0.015 to 100 parts by weight, preferably 0.03 to 80 parts by weight, based on 100 parts by weight of component (A).
    [79] Unsaturated compound (C) comprises at least one olefinic double bond. It may be for example low (monomeric) molecular weight or high (oligomeric) molecular weight. Examples of double bond containing monomers are alkyl or hydroxyalkylacrylates or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate, methyl meta Methacrylate or ethyl methacrylate. Silicone acrylates are also advantageous. Other examples include acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl- and halo Styrene, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride.
    [80] Examples of monomers containing two or more double bonds include ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or diacrylate of bisphenol A, and 4,4'-bis (2-acryloyloxyethoxy) Diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or Tris (2-acryloylethyl) isocyanurate.
    [81] Examples of relatively high molecular weight polyunsaturated compounds (oligomers) are acrylated epoxy resins, acrylated polyesters, vinyl ethers or epoxy group containing polyesters, and polyurethanes and polyethers. Another example of an unsaturated oligomer is an unsaturated polyester resin, usually prepared from maleic acid, phthalic acid and one or more diols, having a molecular weight of about 500 to 3000. In addition, vinyl ether monomers and oligomers can be used, and maleate terminal oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy backbones can also be used. As described in WO 90/01512, combinations of oligomers containing vinyl ether groups and combinations of polymers are particularly suitable. However, copolymers of vinyl ether and maleic acid functionalized monomers are also suitable. Unsaturated oligomers of this type may also be referred to as prepolymers.
    [82] Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids with polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the main or side chains, such as unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, Copolymers containing (meth) acryl groups in the side chain, and two or more such polymers are mixtures.
    [83] Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic acid and methacrylic acid are preferred.
    [84] Suitable polyols are aromatic, in particular aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) propane, and novolacs and resols. Examples of polyepoxides are those based on the polyols, in particular aromatic polyols and epichlorohydrin. Other suitable polyols are polymers and copolymers containing hydroxyl groups in the polymer chain or side chain groups, examples being polyvinyl alcohol and copolymers thereof or polyhydroxyalkyl methacrylates or copolymers thereof. Another suitable polyol is an oligoester having hydroxyl end groups.
    [85] Examples of aliphatic and cycloaliphatic polyols are preferably alkylenediols having 2 to 12 carbon atoms, for example ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1 , 4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2- , 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, di Pentaerythritol and sorbitol.
    [86] The polyols may be partially or fully esterified with one unsaturated carboxylic acid or partially or fully esterified with different unsaturated carboxylic acids, and in some esters the free hydroxy groups may be modified, for example ethers with other carboxyxins. Or esterified.
    [87] Examples of esters include trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate Latent, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate , On Defenta Lithitol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol tris-itaconate, dipentaerythritol pentaitaconate, dipentaerythritol hextaconate, ethylene Glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triarylate, sorbitol tetraacrylate, pentaerythritol-modified tree Acrylate, sorbitol tetra methacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylate and methacrylate, glycerol diacrylate and triacrylate, 1,4-cyclohexane diacrylate, molecular weight 200 Bisacrylate of polyethylene glycol of 1 to 1500 and 'S metadata is a methacrylate or a mixture thereof.
    [88] Also suitable as component (C) are amides of the same or different unsaturated carboxylic acids with aromatic, cycloaliphatic and aliphatic polyamines which preferably have 2 to 6, especially 2 to 4, amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6- Hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediaminephenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine , Di (β-aminoethoxy)-or di (β-aminopropoxy) ethane. Other suitable polyamines are preferably polymers and copolymers having further amino groups in the side chain, and oligoamides having amino terminal groups. Examples of such unsaturated amides are methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamidoethyl methacryl Rate and N [(β-hydroxy-ethoxy) ethyl] acrylamide.
    [89] Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines. Some maleic acid can be replaced with other dicarboxylic acids. They can be used with ethylenically unsaturated comonomers, for example styrene. Polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, in particular diols or diamines having a relatively long chain of 6 to 20 carbon atoms. Examples of polyurethanes are those consisting of saturated or unsaturated diisocyanates and those of unsaturated diols or saturated diols, respectively.
    [90] Polymers having (meth) acrylate groups in the side chain are also known. It may be, for example, a reaction product of a novolak-based epoxy resin with (meth) acrylic acid, or may be a homopolymer or copolymer of a vinyl alcohol or a hydroxyalkyl derivative thereof esterified with (meth) acrylic acid, Homopolymers and copolymers of (meth) acrylates esterified with hydroxyalkyl (meth) acrylates.
    [91] The photopolymerizable compound (C) may be used alone or in a preferred mixture. Preference is given to using mixtures of polyol (meth) acrylates.
    [92] Preferably, component (C) is a monomer having two or more acrylate or methacrylate groups.
    [93] Component (C) is used alone or as a mixture of two or more. Suitable amounts are 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of component (A).
    [94] Organic solvents may also optionally be added to the compositions of the present invention as component (D). Examples of suitable organic solvents include ketones (e.g. ethyl methyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (e.g. toluene, xylene, tetra Methylbenzene, etc.), glycol ethers (e.g. methyl cellosolve, ethyl cellosolve, butyl cellosolve, benzyl cellosolve, phenyl cellosolve, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol monobutyl ether, triethylene glycol monoethyl ether, etc.), esters (e.g. ethyl acetate, butyl acetate, ethyl ethoxypropionate and esterification products of the glycol ethers (e.g. cellosolve acetate, butyl cello) Sorb acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate)], Coles (e.g. ethanol, propanol, n-butanol, n-hexanol, n-heptanol, n-octanol, ethylene glycol, propylene glycol, etc.), aliphatic hydrocarbons (e.g. octane, decane, etc.), petroleum solvents ( Eg petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc.). Organic solvents are used to dilute the resin so that the resin can be easily coated.
    [95] Photopolymerization can also be accelerated by additional addition (as component (E)) of a photosensitizer or coinitiator that changes or broadens the spectral sensitivity. This is especially true for aromatic compounds such as benzophenone and derivatives thereof, thioxanthones and derivatives thereof, anthraquinones and derivatives thereof, coumarins and phenothiazines and derivatives thereof, and 3- (aroylmethylene) thiazoline, rhodanine Camphorquinone, as well as eosin, rhodamine, erythrosine, xanthene, thioxanthene, acridine, for example 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, cyanine and merocyanine dyes.
    [96] Specific examples of such compounds are as follows:
    [97] 1. Thioxanthones:
    [98] Thioxanthone, 2-isopropyl thioxanthone, 2-chloro thioxanthone, 2-dodecyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, 1-methoxy carbonabo Nyl thioxanthone, 2-ethoxycarbonyl thioxanthone, 3- (2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonyl thioxanthone, 3-butoxycarbonyl-7-methyl thi Orcanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl- 3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfuryl thioxanthone, 3,4-di [2- (2-methoxyethoxy) ethoxycarbonyl] -thioxanthone, 1- Ethoxycarbonyl-3- (1-methyl-1-morpholinoethyl) -thioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6- (1,1-dimethoxy Benzyl)-thioxanthone, 2-morpholinomethyl thioxanthone, 2-methyl-6-morpholinomethyl thioxanthone, N-allyl thioxanthone-3,4-dicarboximide, N-octyl thioxanthone-3,4-dicarboximide, N- (1,1,3,3-tetramethylbutyl) -thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylic acid polyethylene glycol ester, 2-hydroxy-3- (3,4 -Dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride;
    [99] 2. Benzophenone:
    [100] Benzophenone, 4-phenyl benzophenone, 4-methoxy benzophenone, 4,4'-dimethoxy benzophenone, 4,4'-dimethyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis (Dimethylamino) -benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-methyl benzophenone, 2,4,6-trimethylbenzophenone, 4- (4-methylthiophenyl) -benzophenone , 3,3'-dimethyl-4-methoxy benzophenone, methyl-2-benzoylbenzoate, 4- (2-hydroxyethylthio) -benzophenone, 4- (4-tolylthio) -benzophenone, 4 -Benzoyl-N, N, N-trimethylbenzenemethanealuminum chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanealuminum chloride monohydrate, 4- (13-Acryloyl-1,4,7,10,13-pentaoxatridecyl) -benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl ) Oxy] ethyl-benzenemethanealuminum chloride;
    [101] 3. Coumarins:
    [102] Coumarin 1, Coumarin 2, Coumarin 6, Coumarin, Coumarin 30, Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337, Coumarin 500, 3-Benzoyl Coumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-dipropoxycoumarin, 3-benzoyl-6,8-dichlorocoumarin, 3- Benzoyl-6-chloro-coumarin, 3,3'-carbonyl-bis [5,7-di (propoxy) -coumarin], 3,3'-carbonyl-bis (7-methoxycoumarin), 3, 3'-carbonyl-bis (7-diethylamino-coumarin), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxy-coumarin, 3-benzoyl-5,7-diethoxy-coumarin , 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di (methoxyethoxy) -coumarin, 3-benzoyl-5,7-di (allyloxy) coumarin, 3-benzoyl- 7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3 -(1-naphthoyl) -coumarin, 5,7-diethoxy-3- (1-naphthoyl) -coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3 -(4-cyanobenzoyl) -5,7-dimethoxycoumarin, 3- (4-cyanobenzoyl) -5,7-dipropoxycoumarin, 7-dimethylamino-3-phenylcoumarin, 7-diethyl Amino-3-phenylcoumarin, coumarin derivatives described in JP 09-179299-A and JP 09-325209-A, for example, 7-[{4-chloro-6 -(Diethylamino) -S-triazin-2-yl} amino] -3-phenylcoumarin;
    [103] 4. 3- (aroylmethylene) -thiazoline:
    [104] 3-methyl-2-benzoylmethylene-β-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-β-naphthothiazoline;
    [105] 5. Rhodanine:
    [106] 4-dimethylaminobenzalotanine, 4-diethylaminobenzalotanine, 3-ethyl-5- (3-octyl-2-benzothiazolinylidene) -rodanine, rhodanine derivatives, Japanese Patent Laid-Open No. 08 Rhodanine of formulas (1), (2) and (7) described in -305019A;
    [107] 6. Other Compounds:
    [108] Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 4,4'-bis (dimethylamino) benzyl, 2-acetylnaphthalene, 2-naphthaldehyde, monocarboxylic acid derivative, 9,10-anthra Quinone, anthracene, pyrene, aminopyrene, perylene, phenanthrene, phenanthrenequinone, 9-fluorenone, dibenzosuberon, curcumin, xanthone, thiomichler's ketone, α- (4-dimethyl Aminobenzylidene) ketones such as 2,5-bis (4-diethylaminobenzylidene) cyclopentanone, 2- (4-dimethylamino-benzylidene) -indan-1-one, 3- (4 -Dimethylamino-phenyl) -1-indan-5-yl-propenone, 3-phenylthioptalimide, N-methyl-3,5-di (ethylthio) -phthalimide, N-methyl-3 , 5-di (ethylthio) -phthalimide, phenothiazine, methylphenothiazine, amine, for example N-phenylglycine, ethyl 4-dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate , 4-dimethylaminoacetophenone, tri Olamine, methyl diethanolamine, dimethylaminoethanol, 2- (dimethylamino) ethyl benzoate, p- dimethylaminobenzoate.
    [109] The action of the amines can be enhanced by the addition of benzophenone based aromatic ketones. An example of an amine that can be used as an oxygen scavenger is the substituted N, N-dialkylaniline described in EP 339841. Other promoters, co-initiators and autoxdizers are thiols, thioethers, disulfides, phosphonium salts, phosphine oxides, as described in EP 438123, GB 2180358 and JP Kokai Hei 6-68309. Or phosphine.
    [110] In some cases, it may be advantageous to use a sensitizer compound with Compound (B). Thus, another object of the present invention is, in addition to components (A), (B) and (C), one or more photosensitizer compounds (E), in particular benzophenone and derivatives thereof, thioxanthones and derivatives thereof, anthra In a composition comprising a compound selected from the group consisting of quinones and derivatives thereof, or coumarins and derivatives thereof.
    [111] In addition to components (A) to (E), the photopolymerizable mixture may comprise a thermosetting component (F).
    [112] Examples of component (F) are compounds having an epoxy group as the thermosetting component. For example, solid or liquid known epoxy compounds can be used, which epoxy compounds are used according to the required properties. For example, when the plating resistance should be improved, a liquid epoxy resin is used, and when water resistance is required, an epoxy resin having a plurality of methyl groups in the benzene ring or the cycloalkyl ring is used. Preferred epoxy resins are bisphenol S type epoxy resins such as BPS-200 (Nippon Kayaku Co.), EPX-30 (ACR Co.), Epiculon EXA-1514 (Dainippon Ink & Chemicals Inc.). ) Etc; Bisphenol A type epoxy resin, for example, Epiculon N-3050, N-7050, N-9050, Dainippon Ink & Chemicals Inc., XAC-5005, GT-7004, 6484T, 6099, Asahi Kasei Epoxy Co., Ltd.); Bisphenol F type epoxy resins such as YDF-2004, YDF2007 (Tohto Kasei C.), and the like; Diglycidyl phthalate resins such as Blemmer DGT (Nippon Oil and Fats Co., Ltd.) and the like; Heterocyclic epoxy resins such as TEPIC (Nissan Chemical Industries, Ltd.), Araldite PT810 (Asahi Kasei Epoxy Co., Ltd), and the like; Bixyleneol-based epoxy resins such as YX-4000 (manufactured by Yuka Shell Co.) and the like; Bisphenol-based epoxy resins such as YL-6056 (Yuka shell Co.) and the like; Tetraglycidyl xyleneol ethane resins such as ZX-1063 (Tohto Kasei Co.) and the like; Novolak-based epoxy resins such as EPPN-201, EOCN-103, EOCN-1020, EOCN-1025 and BRRN from Nippon Kayaku Co., Ltd., ECN-278, ECN-292 and ECN-299 (Manufacturer: Asahi Kasei Epoxy Co., Ltd.), GY-1180, ECN-1273 and ECN-1299 (Manufacturer: Asahi Kasei Epoxy Co., Ltd.), YDCN-220L, YDCN-220HH, YDCN-702, YDCN -704, YDPN-601 and YDPN-602 from Tohto Kasei Co., Epiculon-673, N-680, N-695, N-770 and N-775 from Dainippon Ink & Chemicals Inc .; Novolac epoxy resins of bisphenol A, for example EPX-8001, EPX-8002, EPPX-8060 and EPPX-8061 (manufactured by Asahi Kasei Epoxy Co., Ltd), Epiculon N-880 (manufactured by Dainippon Ink & Co., Ltd.) Chemicals Inc.) and the like; Chelate epoxy resins such as EPX-49-69 and EPX-49-30 (manufactured by Asahi Denka Kogyo K.K.) and the like; Glyoxal epoxy resins such as YDG-414 (manufactured by Tohto Kasei Co.) and the like; Amino group-containing epoxy resins such as YH-1402 and ST-110 (Tohto Kasei Co.), YL-931 and YL-933 (Yuka Shell Co.) and the like; Rubber modified epoxy resins such as Epiculon TSR-601 from Dainippon Ink & Chemicals Inc., EPX-84-2 and EPX-4061 from Asahi Denka Kogyo K.K. Dicyclopentadiene phenolic epoxy resins such as DCE-400 manufactured by Sanyo-Kokusaku Pulp Co., Ltd .; Silicone modified epoxy resins such as X-1359 from Asahi Denka Kogyo KK e-caprolactone modified epoxy resins such as Plaque G-402 and G-710 from Dicel Chemical Industries, Ltd.). In addition, compounds that are partially esterified (eg, esterified with (meth) acrylate) of these epoxy compounds may be used together.
    [113] Preferably, the thermosetting component is bisphenol A, bisphenol S, bisphenol F or novolac epoxy compound.
    [114] A suitable amount of the thermosetting component (F) to be used according to the present invention is 10 to 150 parts by weight, preferably 20 to 80 parts by weight based on 100 parts by weight of the component (A).
    [115] Accordingly, the present invention also relates to compositions comprising at least one compound (F) having an epoxy group in addition to component (A), component (B) and component (C).
    [116] In addition to the components (A), (B) and (C) as well as components (D), (E) and (F), various additives (G) are present in the present invention in amounts conventional in the art. It can be used in the composition according to.
    [117] In the photosensitive thermosetting resin composition of the present invention, in order to improve properties such as adhesive properties, curability, and the like, an inorganic filler (G1), for example, barium sulfate, barium titanate, silicon oxide powder, particulate silicon oxide, Amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder, and the like. The proportion of filler in the formulation is 0 to 60% by weight, preferably 5 to 40% by weight of the photosensitive thermosetting resin composition.
    [118] The composition of the present invention optionally further comprises a cure accelerator such as an amine compound, an imidazole compound, a carboxylic acid, a phenol, a quaternary ammonium salt or a methylol group containing compound as component (G2). The range of the amount of the curing agent used is 0 to 10% by weight, preferably 0.05 to 5% by weight of the photosensitive thermosetting resin composition.
    [119] Examples of additional additives (G) are heat inhibitors to prevent premature polymerization, examples of which are hydroquinones, hydroquinone derivatives, p-methoxyphenols, β-naphthol or sterically hindered phenols such as 2,6-di- Tert-butyl-p-cresol). To increase storage stability in the dark, for example, copper compounds (eg copper naphthenate, stearate or octoate), phosphorus compounds (eg triphenylphosphine, tributylphosphine, triethyl phosphite , Triphenyl phosphite or tribenzyl phosphite), quaternary ammonium compounds (eg tetramethylammonium chloride or trimethylbenzylammonium chloride) or hydroxylamine derivatives (eg N-diethylhydroxylamine) can be used. To exclude atmospheric oxygen during the polymerization, paraffin or similar waxy materials may be added that suitably dissolve in the polymer and migrate to the surface at the beginning of the polymerization to form a transparent surface layer that prevents the introduction of air. In addition, an oxygen impermeable layer can be applied. Light stabilizers that can be added in small amounts are UV absorbers, for example hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxalamide or hydroxyphenyl-s-triazine based UV absorbers. These compounds can be used individually or as mixtures with or without sterically hindered amines (HALS).
    [120] Examples of such UV absorbers and light stabilizers (G3) are as follows:
    [121] 1. 2- (2'-hydroxyphenyl) benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-3 Tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tertiary-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1, 1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- ( 3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2'-hydride Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) Benzotriazole, 2- (3 ', 5'-bis- (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2' -Hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5'-[2- (2-ethylhexyloxy ) Carbonylethyl] -2'-hydroxyphenyl) -5- Lorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'- Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxy Phenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5'- A mixture of (2-isooctyloxycarbonylethyl) phenylbenzotriazole, and 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazole-2 -Yl-phenol]; transesterification of 2- [3'-tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -benzotriazole with polyethylene glycol 300 reaction product; [R-CH 2 CH 2 -COO (CH 2) 3] 2 - ( wherein, R represents 3'-tert-butyl-4'-hydroxy -5'-2H- benzo agent 2-yl-phenyl).
    [122] 2. 2-hydroxybenzophenones such as 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy- , 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.
    [123] 3. Esters of substituted or unsubstituted benzoic acid, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert- Butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-3 Tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5- Di-tert-butyl-4-hydroxybenzoate.
    [124] 4. Acrylate, such as isooctyl or ethyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, butyl or methyl α-cyano-β-methyl-p- Methoxycinnamate, methyl α-carboxymethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindolin.
    [125] 5. sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis- (2,2,6,6-tetramethylpiperidyl) succinate, bis -(1,2,2,6,6-pentamethylpiperidyl) sebacate, bis- (1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di- Condensation product of tert-butyl-4-hydroxybenzylmalonate, 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis Condensation of-(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine Product, tris- (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1, 2,3,4-butane tetraoate, 1,1 '-(1,2-ethanediyl) bis (3,3,5,5-tetramethyl-piperazinone), 4-benzoyl-2,2, 6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2,6,6-penta Methylpiperidyl) 2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl -1,3,8-triazaspiro- [4.5] -decane-2,4-dione, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene Condensation product of diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-di- (4-n-butylamino-2,2,6, Condensation product of 6-tetramethylpiperidyl) -1,3,5-triazine with 1,2-bis- (3-aminopropyl-amino) ethane, 2-chloro-4,6-di- (4-n Condensation products of -butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine with 1,2-bis- (3-aminopropylamino) -ethane, 8- Condensation product of acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2 , 2,6,6-tetramethyl-4-pipe Dill) pyrrolidine-2,5-dione and 3-dodecyl-1- (1,2,2,6,6-penta-methyl-4-piperidyl) -pyrrolidine-2,5-dione .
    [126] 6. Oxalamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert- Butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis- (3 -Dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl Mixtures of oxanilides, mixtures of o-methoxy-disubstituted oxanalides and p-methoxy-disubstituted oxanalides, and o-ethoxy-disubstituted oxanalides and p-ethoxy-disubstituted Mixture with oxanalide.
    [127] 7. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5 -Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4- Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxy-phenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5- Triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethyl-phenyl) -1,3,5-triazine, 2- [2-hydroxy -4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-dodecyl / Tridecyl-oxy- (2-hydroxypropyl) oxy-2-hydroxy-phenyl] -4,6-bis (2,4-dimethylfe ) 1,3,5-triazine.
    [128] 8. phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, Distearyl pentaerythryl diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythryl diphosphite, bis- (2,4-di-tert-butyl Phenyl) pentaerythryl diphosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) pentaerythryl diphosphite, bis-isodecyloxy pentaerythryl diphosphite, bis- ( 2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis- (2,4,6-tri-tert-butylphenyl) pentaerythryl diphosphite, tristearyl sorbate Bityl triphosphite, tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4, 8,10-tetra-tert-butyl-12H-di-benzo [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tertiary -Butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphosine, bis- (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis ( 2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.
    [129] Accordingly, the present invention also relates to a composition comprising at least one UV absorber or light stabilizer compound (G3) in addition to component (A), component (B) and component (C).
    [130] Also, if desired, known additives such as phthalocyanine blue, phthalocyanine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black and the like can be used.
    [131] Accordingly, the subject of the present invention is such a composition further comprising an additive (G), in particular an inorganic filler, selected from the group consisting of inorganic fillers, colorants, dispersants, heat curing inhibitors, thickeners, antifoams and leveling agents.
    [132] In addition, chain transfer agents customary in the art can be added to the compositions according to the invention. Examples are mercaptans, amines and benzothiazoles.
    [133] The curing process is carried out in particular for components which form free radicals under thermal conditions, for example azo compounds [e.g. 2,2'-azobis (4-methoxy-2,4, described in European Patent No. 2456392). Dimethylvaleronitrile), triazene, diazo sulfide, pentazadiene] or peroxy compounds such as hydroperoxide or peroxycarbonate (eg t-butyl hydroperoxide) (eg And titanium dioxide).
    [134] The composition according to the invention can be used as a further additive (G) as a photoreducable dye, for example xanthene, benzoxanthene, benzothioxanthene, thiazine, pyranine, porphyrin or acridine dye, and / Or a trihalogenmethyl compound that can be cleaved by light irradiation. Similar compositions are described, for example, in European Patent No. 445624.
    [135] Further conventional additives (G), depending on the intended use, are fluorescent brighteners, wetting agents or bacteriologic aids.
    [136] In order to cure thick colored coatings, it is suitable to add glass microspheres or pulverized glass fibers, as described, for example, in US Pat. No. 5,013,768.
    [137] Additive (G) is selected according to the application and the properties required in the art. Such additives are conventional in the art and are therefore added in amounts useful for the respective application.
    [138] In certain cases, mixtures with known photoinitiators (B1), for example camphor quinone, benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, for example α-hydroxycycloalkyl phenyl ketones or 2-hydroxy Oxy-2-methyl-1-phenyl-propanone, dialkoxyacetophenone, α-hydroxy- or α-aminoacetophenone, for example (4-methylthiobenzoyl) -1-methyl-1-morpholi Noethane, 4-oroyl-1,3-dioxolane, benzoin alkyl ethers and benzyl ketals such as dimethyl benzyl ketal, phenylglyoxalic acid esters and derivatives thereof, dimeric phenylglyoxalic acid esters, diacetyl, per Esters such as the benzophenone tetracarboxylic acid perester described in European Patent No. 126541, monoacyl phosphine oxides such as (2,4,6-trimethylbenzoyl) diphenylphosphine oxide, bisacylphosphine Oxide, bis (2,6-dimethoxy-benzoyl )-(2,4,4-trimethyl-pentyl) phosphine oxide, bis (2,4,6-trimethyl-benzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4 -Dipentoxyphenylphosphine oxide, trisacylphosphine oxide, oxime esters, for example 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-phenyl-1,2-propanedione 2-O-ethoxycarbonyl oxime, halomethyltriazine, for example 2- [2- (4-methoxy-phenyl) -vinyl] -4,6-bis-trichloromethyl- [1,3 , 5] triazine, 2- (4-methoxy-phenyl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (3,4-dimethoxy-phenyl)- 4,6-bis-trichloromethyl- [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (4-N , N-di (ethoxycarbonylmethyl) -aminophenyl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (4-methoxy-naphthyl) -4, 6-bis-trichloromethyl- [1,3,5] triazine, 2- (1,3-benzodioxol-5-yl) -4,6-bis-trichloromethyl- [1,3,5 ] Lysine, 2- [2- [4- (pentyloxy) phenyl] ethenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2- (3-methyl -2-furanyl) -ethenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2- (5-methyl-2-furanyl) -ethenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2- (2,4-dimethoxy-phenyl) -ethenyl] -4,6-bistrichloromethyl- [1,3,5] triazine, 2- [2- (2-methoxy-phenyl) ethenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [ 2- [4-isopropyloxy-phenyl] -ethenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2- (3-chloro-4-methoxy -Phenyl) ethenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2-bromo-4-N, N-di (ethoxycarbonylmethyl) amino -Phenyl] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [2-chloro-4-N, N-di (ethoxycarbonylmethyl) amino-phenyl]- 4,6-bis-trichloromethyl- [1,3,5] triazine, 2- [3-bromo-4-N, N-di (ethoxycarbonylmethyl) amino-phenyl] -4,6 - Th-trichloromethyl- [1,3,5] triazine, 2- [3-chloro-4-N, N-di (ethoxycarbonylmethyl) amino-phenyl] -4,6-bis-trichloro Methyl- [1,3,5] triazine, or G. Buhr, R. Dammel and C. Lindley Polym. Mater. Sci. Eng. 61,129 (1989), and EP 0262788; Halomethyl-oxazole photoinitiators described in US Pat. No. 4,371,606 and US Pat. No. 4,371,607; 1,2-disulfones described in E. A. Bartmann, Synthesis 5, 490 (1993); Hexaarylbisimidazole and hexaarylbisimidazole / initiator systems, for example ortho-chlorohexaphenyl-bisimidazole, ferrocenium compounds, or titanocene in combination with 2-mercaptobenzothiazole, for example For example, it is advantageous to use bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium.
    [139] When the new system is used as a hybrid system, cationic photoinitiators, peroxide compounds, such as benzoyl peroxide (other suitable peroxides, in addition to free radical curing agents, are described in US Pat. No. 4,950,581, column 19, lines 17 to 25). ), And the aromatic sulfonium, phosphonium or iodonium salts or cyclopentadienyl-arene-iron described in US Pat. No. 4,950,581 (column 18, line 60 to column 19, line 10). II) complex salts, for example (η 6 -iso-propylbenzene) (η 5 -cyclopentadienyl) iron (II) hexafluorophosphate as well as for example oximes described in EP 780729 Sulfonic acid esters are used. For example, the pyridinium and (iso) quinolinium salts described in EP 497531 and EP 441232 can be used with the novel photoinitiators.
    [140] Accordingly, the subject of the present invention is a composition further comprising one or more photoinitiators (B1).
    [141] Further photoinitiator as component (B1) is added in an amount of from 0.015 to 80 parts by weight, preferably 0.03 to 60 parts based on 100 parts by weight of component (A).
    [142] The present invention also relates to a composition comprising 100 parts by weight of component (A), 0.015 to 100 parts by weight of component (B), 5 to 200 parts by weight of component (C) and 0.015 to 80 parts by weight of component (E).
    [143] The compositions of the invention are known coating methods, for example spin coating, immersion coating, knife coating, curtain coating, screen coating, brush spray, in particular electrostatic spray and reverse-roll coating. coating is uniformly applied to the substrate, and by electrophoretic attachment means. The photosensitive layer may be applied to a temporary soft support, and then the final substrate, for example a copper-clad circuit board, may be coated by moving the layer through lamination.
    [144] The amount applied (coat thickness) and the nature of the substrate (layer support) depend on the desired application. The coating thickness ranges generally from about 0.1 μm to 10 mm, for example from 0.1 μm to 1 mm, preferably from 0.3 μm to 200 μm.
    [145] After coating the substrate, the solvent is generally removed by drying to leave a photoresist film on the substrate.
    [146] The term "imagewise" exposure is carried over a surface of a photomask comprising a predetermined pattern, for example a slide, a chromium mask, a stencil mask or a reticle, as well as a substrate coated for example under computer control. And exposure through a laser or light beam to produce an image in this way. Computer controlled irradiation can also be achieved by electron beams. See also, A. Bertsch, J.Y. Jezequel, J.C. Andre, Journal of Photochemistry and Photobiology A: Chemistry 1997, 107, p. 275-281 and by K.P. Nicolay in Offset Printing 1997, 6, p. 34-37, a mask made of liquid crystal that can be addressed with a pixel by pixel to generate a digital image can be used.
    [147] The photosensitivity of the novel compositions can generally be extended to about 190 nm to 600 nm (UV to visible light region). Suitable radiation is, for example, present in light from a sun or artificial light source. As a result, many very different types of light sources are used. Both point sources and arrays (“lamp carpets”) are suitable. Examples include carbon arc lamps, xenon arc lamps, medium, high, ultra high and low pressure mercury lamps, possibly lamps with metal halide dope (metal halide lamps), microwave stimulating metal vapor lamps, excimer lamps, superactin Superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, electric flashlights, photographic flood lamps, luminescent biodes (LEDs), electron beams and X-rays. According to the invention the distance between the lamp and the exposed substrate can vary depending on the intended use and the type and output of the lamp, for example 2 cm to 150 cm. Also suitable are laser light sources such as excimer lasers (eg Krypton F lasers for exposure at 248 nm). Lasers in the visible range can also be used. The UV laser exposure system (DP-100 TM DIRECT IMAGINGSYSTEM) from Etec and Orbotech is suitable for UV laser direct imaging without the use of photomasks.
    [148] Accordingly, the present invention also provides a method for photopolymerizing a compound containing ethylenically unsaturated double bonds, including irradiating the composition with electromagnetic radiation in the range from 190 to 600 nm.
    [149] As already mentioned, the composition may be manifested by an aqueous alkali. Particularly suitable aqueous alkaline developer solutions are aqueous solutions of tetraalkylammonium hydroxides or aqueous solutions of alkali metal silicates, phosphates, hydroxides and carbonates. Small amounts of wetting agents and / or organic solvents may also be added to these solutions, if desired. Examples of conventional organic solvents that can be added in small amounts to the developer solution are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of these solvents.
    [150] The composition of the present invention is particularly suitable for aqueous developable photoresist applications due to its excellent sensitivity and developability. They are also excellent in thermal stability.
    [151] The novel radiation sensitive compositions are used as negative resists which are very sensitive to light and can be developed without swelling in an aqueous alkaline solution. It is suitable as a photoresist for electronics such as electroplating resists, etch resists, liquid and dry films, solder resists, or for producing color filters for various display articles or for plasma display panels and electroluminescence As a resist that creates structures in the display manufacturing process, it is suitable for use in fitness, printing plates (eg offset printing or screen printing), relief printing, flat printing, manufacturing printing forms for gravure printing, or manufacturing and stamping screen printing foams. Suitable for manufacturing, suitable for use in chemical grinding or as a microresist in the manufacture of integrated circuits. The composition of the present invention may further be used as a light patternable dielectric layer or coating, encapsulation material and separation coating in the manufacture of computer chips, printing plates and other electrical or electronic components. The processing conditions of possible layer supports and coated substrates vary.
    [152] Since the photocurable compositions according to the invention have good developability and high sensitivity to UV light, they are particularly suitable for the production of color filters or color mosaic systems, for example as described in EP 320 264. Do. Color filters are commonly used in the manufacture of LC displays, projection systems and image sensors. Color filters can be used for display and image scanners, for example in television receivers, video monitors or computers, and in flat panel display technologies and the like.
    [153] In the process of forming the color filter, red, green and blue coloring materials, dyes and pigments are added to the photosensitive resin composition of the present invention to provide a photosensitive resin composition layer of a specific color on the transparent substrate, and then usually the color filter from the coating side. It is exposed through a photomask having a pattern, developed with a suitable alkaline developing solution, and optionally heated. The process is repeated to form an image having a plurality of colors.
    [154] In the photosensitive resin composition of the present invention, in the case of using a process of forming at least one picture element on a transparent substrate and then exposing it from a side surface of the transparent substrate on which the pixel is not formed, the pixel is a light shielding mask. It can be used as a light-shielding mask. In such a case, for example, in the case of full exposure, the positional adjustment of the mask becomes unnecessary and there is no interest in its positional deviation. And all the parts in which the said pixel is not formed can be hardened. Further, in such a case, it is also possible to develop and remove a part of the portion where the above pixel is not formed by partially using the light shielding mask.
    [155] In either case, since no gap is formed between the first formed pixel and the later formed pixel, the composition of the present invention is suitable, for example, for forming materials for color filters. Specifically, red, green and blue colored materials, dyes and pigments are added to the photosensitive resin composition of the present invention, and the image forming process is repeated to form red, green and blue pixels. Subsequently, the photosensitive resin composition to which the black coloring material, dye, and a pigment were added is provided to the whole surface, for example. This is totally exposed (or partially exposed through a light shielding mask) to form black pixels in the entire space between the red, green and blue pixels.
    [156] In addition to the method of coating and drying the photosensitive resin composition on a substrate, the photosensitive resin composition of the present invention may also be used for the layer transfer material. That is, the photosensitive resin composition is provided layered directly on a temporary support, preferably on a polyethylene terephthalate film, or on a polyethylene terephthalate film provided with an oxygen shielding layer and a peeling layer or a peeling layer and an oxygen shielding layer thereon. Usually, a removable cover sheet made of synthetic resin is laminated thereon for protection in handling. It is also possible to use a layer structure in which the alkali-soluble thermoplastic resin layer and the intermediate layer are removed on the temporary support and further provided with the photosensitive resin composition layer thereon (Japanese Patent Laid-Open No. 5-173320-A).
    [157] The cover sheet is removed in use and the photosensitive resin composition layer is laminated on the permanent support. Then, if an oxygen shielding layer and a peeling layer are provided, peeling is performed between these layers and the temporary support, and if a peeling layer and an oxygen shielding layer are provided, peeling is performed between the peeling layer and the oxygen shielding layer. And, if no release layer or oxygen shielding layer is provided, peeling is performed between the temporary support and the photosensitive resin composition and the temporary support is removed.
    [158] Various dispersion means, such as a three roll mill, a sand mill, a ball mill, a kneader, and a paint shaker, are used to produce a photosensitive coloring composition. The composition is generally applied to the substrate using a coating method such as spray coating, spin coating, roll coating or screen coating. Light sources such as ultra-high pressure mercury lamps or metal halides are commonly used for irradiation.
    [159] Glass supports, metals, ceramics and synthetic resin films can be used as the support for color filters. Particularly preferred are glass and synthetic resin films that are transparent and have excellent dimensional stability.
    [160] The thickness of the photosensitive resin composition for color filters is 0.1-10 micrometers normally, especially 0.3-5 micrometers.
    [161] Also included are solutions prepared by using a diluted aqueous solution of an alkaline substance as the developing solution for the photosensitive resin composition of the present invention, and adding a small amount of a water miscible organic solvent thereto.
    [162] Examples of suitable alkali materials include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, alkali metal silicates such as Sodium silicate and potassium silicate), alkali metal metasilicates (e.g. sodium metasilicate and potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (e.g. tetramethylammonium hydroxide Rockside) or trisodium phosphate. The concentration of the alkaline substance is from 0.01 to 30% by weight, and the pH is preferably from 8 to 14.
    [163] Suitable organic solvents that are miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl Alcohol, acetone, methyl ethyl ketone, cyclohexanone, epsilon-caprolactone, gamma-butyrolactone, dimethylformamide, dimethylacetoamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, epsilon-caprol Lactam and N-methyl-pyrrolidone. The concentration of organic solvents miscible with water is from 0.1 to 30% by weight.
    [164] It is also possible to add surfactants known to those skilled in the art. The concentration of the surfactant is preferably 0.001 to 10% by weight.
    [165] The developing solution may be used in the form of a bath solution or a spray solution. To remove the uncured portion of the sensitive resin composition layer, a method of rubbing with a rotary brush and a method of rubbing with a wet sponge can be combined. Usually, the temperature of a developing solution becomes like this. Preferably it is room temperature-40 degreeC. The developing time may vary depending on the temperature of the particular type of photosensitive resin composition, the alkali and the developing solution, and when the organic solvent is added, may also vary depending on the type and concentration of the organic solvent. Usually 10 seconds to 1 minute. The cleaning step may be performed following the developing process.
    [166] The final heat treatment is preferably carried out after the developing process. Thus, a support (hereinafter referred to as a photocured layer) with a layer photopolymerized by exposure is heated in an electric furnace and a dryer, or the photocured layer is irradiated with an infrared lamp or heated on a hot plate. The heating temperature and time depends on the composition used and the thickness of the layer formed. In general, heating is preferably performed at about 120 to about 260 ° C. for about 5 to about 60 minutes.
    [167] Pigments which can be included in the compositions according to the invention, including colored color filter resist compositions, are preferably processed pigments, for example pigments with acrylic resins, vinyl chloride-vinyl acetate copolymers, maleic acid resins and ethyl. Powder or paste product prepared by fine dispersion in one or more resins selected from the group consisting of cellulose resins.
    [168] The red pigment is, for example, an anthraquinone pigment alone, a perylene pigment alone or a mixture consisting of one or more thereof and a disazo yellow pigment or isoindolin yellow pigment, in particular C.I. Pigment Red 177 alone, C.I. Pigment Red 155 and C.I. Pigment Yellow 83 or C.I. Pigment Yellow 139 (“C.I.” is a color index known and publicly available to those skilled in the art). Examples of further suitable pigments include C.I. Pigment Red 105, 144, 149, 176, 177, 185, 202, 209, 214, 222, 242, 254, 255, 264, 272 and C.I. Pigment Yellow 24, 31, 53, 83, 93, 95, 109, 110, 128, 129, 138, 139, 166 and C.I. Pigment Orange 43.
    [169] The green pigments are, for example, halogenated phthalocyanine pigments alone or mixtures thereof with disazo yellow pigments or isoindolin yellow pigments, in particular C.I. Pigment Green 7 alone, C.I. Pigment Green 36 alone, C.I. Pigment Green 37 alone, or C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 37, C.I. Pigment Green 136 and C.I. Pigment Green 38 and C.I. And mixtures of one or more members of Pigment Green 139.
    [170] Examples of suitable blue pigments are phthalocyanine-based pigments used alone or in combination with dioxazine-based violet pigments such as C.I. Pigment Blue 15: 3 and C.I. It is a combination with Pigment Violet 23. Further examples of blue pigments include C.I. Blue 15: 3, 15: 4, 15: 6, 16 and 60, ie phthalocyanine C.I. Pigment Blue 15: 3 or phthalocyanine C.I. Pigment Blue 15: 6. Other suitable pigments are C.I. Pigment Blue 22, 28, C.I. Pigment Violet 14, 19, 23, 29, 32, 177 and C.I. Orange 73.
    [171] The pigment of the black matrix photopolymeric composition preferably comprises at least one member selected from the group consisting of carbon black, titanium black and iron oxide. However, mixtures of other pigments which give a totally black appearance can also be used. For example, C.I. Pigment Black 1 and 7 can also be used alone or in combination.
    [172] For certain colors, a combination of two or more pigments may also be used. Particularly suitable for color filter compositions are powdered processed pigments prepared by finely dispersing the pigments mentioned above in a resin.
    [173] The concentration range of the pigment in the total solid component is, for example, 5 to 80% by weight, in particular 10 to 50% by weight.
    [174] The median particle diameter of the pigment in the color filter resist composition is preferably smaller than the wavelength of visible light (400-700 nm). The intermediate pigment diameter is particularly preferably less than 100 nm.
    [175] If desired, the pigment may be stabilized in the photosensitive composition by pretreatment of the pigment with a dispersant to improve the dispersion stability of the pigment in the liquid formulation.
    [176] Examples of dispersants are, for example, commercially available compounds described in JP-A-10-90891, for example, EFKA-46, EFKA-47, S 3000, S 5000, S 22000 and S 24000.
    [177] Preferably, the color filter resist composition according to the invention further contains at least one addition polymerizable monomeric compound.
    [178] For example, the following compounds may be used alone or in combination with other monomers as the addition polymerizable monomer having an ethylenically unsaturated double bond used in the present invention. Specifically, these include tert-butyl (meth) acrylate, ethylene glycol di (meth) acrylate, 2-hydroxypropyl (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri ( Meth) acrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylic Latex, dipentaerythritol penta (meth) acrylate, polyoxyethylated trimethylolpropane tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 1,4-di Isopropenyl-benzene, 1,4-dihydroxybenzene (meth) acrylate, decamethylene glycol di (meth) acrylate, styrene, diallyl fumarate, triallyl trimellitate, lauryl (meth) acrylate , (Meth) acrylamide and xylenebis (meth) acrylamide. In addition, compounds having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and polyethylene glycol mono (meth) acrylate] and diisocyanates such as hexamethylene Reaction products with diisocyanates, toluene diisocyanates and xylene diisocyanates) can be used. Particular preference is given to pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipenta-erythritol pentaacrylate and tris (2-acyloyloxyethyl) -isocyanurate.
    [179] In the color filter resist composition, the total amount of monomers contained in the photopolymerizable composition is preferably 5 to 80% by weight, in particular 10 to 70% by weight, based on the total solid components of the composition.
    [180] A binder for use in color filter resist compositions that are soluble in aqueous alkali solutions and insoluble in water, wherein the homopolymer of a polymerizable compound having at least one acid group and at least one polymerizable unsaturated bond in a molecule, or two or more copolymers thereof And copolymers of one or more polymerizable compounds having at least one unsaturated bond copolymerizable with these compounds and containing no acid groups. Such compounds include at least one low molecular weight compound having at least one acidic group and at least one polymerizable unsaturated bond in the molecule, and at least one polymerizable compound having at least one unsaturated bond that is vacable with these compounds and containing no acid groups. Can be obtained by copolymerization. Examples of acid groups are COOH group, -SO 3 H group, -SO 2 NHCO- group, phenolic hydroxy group, -SO 2 NH- group and -CO-NH-CO- group. Among these, high molecular weight compounds having a -COOH group are particularly preferred.
    [181] Examples of polymerizable compounds having at least one acid group and at least one polymerizable unsaturated bond in the molecule include in particular the following compounds:
    [182] Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinylbenzoic acid and cinnamic acid are examples of polymerizable compounds having at least one -COOH group and at least one polymerizable unsaturated bond in the molecule.
    [183] Vinylbenzenesulfonic acid and 2- (meth) acrylamide-2-methylpropanesulfonic acid are examples of polymerizable compounds having at least one unsaturated bond with at least one —SO 3 H group.
    [184] N-methylsulfonyl (meth) acrylamide, N-ethylsulfonyl (meth) acrylamide, N-phenylsulfonyl (meth) acrylamide and N- (p-methylphenylsulfonyl) (meth) acrylamide are one or more Examples of polymerizable compounds having at least one polymerizable unsaturated bond with a —SO 2 NHCO— group.
    [185] Examples of polymerizable compounds having at least one phenolic hydroxy group and at least one polymerizable unsaturated bond in the molecule include hydroxyphenyl (meth) acrylamide, dihydroxyphenyl (meth) acrylamide, hydroxyphenyl-carbonyloxy Ethyl (meth) acrylate, hydroxyphenyloxyethyl (meth) acrylate, hydroxyphenylthioethyl (meth) acrylate, dihydroxyphenylcarbonyloxyethyl (meth) acrylate, dihydroxyphenyloxyethyl ( Meth) acrylate and dihydroxy-phenylthioethyl (meth) acrylate.
    [186] Examples of polymerizable compounds having at least one -SO 2 NH- group and at least one polymerizable unsaturated bond in the molecule are compounds of formula a or b.
    [187] CH 2 = CHA 1 -Y 1 -A 2 -SO 2 -NH-A 3
    [188] CH 2 = CHA 4 -Y 2 -A 5 -NH-SO 2 -A 6
    [189] In the above formulas a and b,
    [190] Y 1 and Y 2 are each -COO-, -CONA 7 -or a single bond,
    [191] A 1 and A 4 are each H or CH 3 ,
    [192] A 2 and A 5 are each optionally or C 1 -C 12 alkylene, cycloalkylene, arylene or aralkylene having a substituent, with the ether group and a thioether group are inserted C 2 -C 12 alkylene, cyclohexylene Alkylene, arylene or aralkylene,
    [193] A 3 and A 6 are each H, optionally substituted C 1 -C 12 alkyl, a cycloalkyl group, an aryl group or an aralkyl group,
    [194] A 7 is H, optionally substituted C 1 -C 12 alkyl, cycloalkyl group, aryl group or aralkyl group.
    [195] Polymerizable compounds having at least one -CO-NH-CO- group and at least one polymerizable unsaturated bond include maleimide and N-acryloyl-acrylamide. These polymeric compounds become high molecular weight compounds containing a -CO-NH-CO- group, where a ring is formed together with a main chain by polymerization. In addition, methacrylic acid derivatives and acrylic acid derivatives each having a -CO-NH-CO- group can also be used. As such methacrylic acid derivatives and acrylic acid derivatives, for example, methacrylamide derivatives (e.g., N-acetylmethacrylamide, N-propionyl methacrylamide, N-butanoylmethacrylamide, N-pentanoylmetha) Krillamide, N-decanoyl methacrylamide, N-dodecanoyl methacrylamide, N-benzoyl methacrylamide, N- (p-methylbenzoyl) methacrylamide, N- (p-chlorobenzoyl) methacrylamide , N- (naphthyl-carbonyl) methacrylamide, N- (phenylacetyl) -methacrylamide and 4-methacryloylaminophthalimide), and acrylamide derivatives having the same substituents. These polymerizable compounds are polymerized into compounds having a —CO—NH—CO— group in the side chain.
    [196] Examples of polymerizable compounds having at least one polymerizable unsaturated bond and containing no acid groups are selected from (meth) acrylates, ((meth) acrylamides, acrylic compounds, vinyl ethers, vinyl esters, styrenes and crotonates, There are compounds with polymerizable unsaturated bonds, specifically (meth) acrylates such as alkyl (meth) acrylates or substituted alkyl (meth) acrylates [e.g. methyl (meth) acrylate, ethyl (meth ) Acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, ethylhexyl (Meth) acrylate, octyl (meth) acrylate, t-octyl (meth) acrylate, chloro-ethyl (meth) acrylate, allyl (meth) acrylate, 2- Hydroxy-ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2,2-dimethyl-3-hydroxy-propyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, benzyl (meth) acrylate, methoxy-benzyl (meth) acrylate, chlorobenzyl (Meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate], and aryl (meth) acrylate [eg phenyl (meth) acrylate , Cresyl (meth) acrylate and naphthyl (meth) acrylate; (meth) acrylamides such as (meth) acrylamide, N-alkyl (meth) acrylamide (as alkyl group, for example For example, methyl, ethyl, propyl, Butyl, t-butyl, heptyl, octyl, ethylhexyl, cyclohexyl, hydroxy-ethyl and benzyl), N-aryl (meth) acrylamide (as aryl groups, for example, phenyl, tolyl, nitrophenyl , Naphthyl and hydroxyphenyl), N, N-dialkyl (meth) acrylamide (alkyl groups include, for example, methyl, ethyl, butyl, isobutyl, ethylhexyl and cyclohexyl), N, N-diaryl (meth) acrylamide (as aryl group, for example, there is phenyl), N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth ) Acrylamide, N-2-acetoamide ethyl-N-acetyl (meth) acrylamide, N- (phenyl-sulfonyl) (meth) acrylamide and N- (p-methylphenyl-sulfonyl) (meth) acrylamide ; Allyl compounds such as allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate and allyl lactate Allyloxyethanol; Vinyl ethers, such as alkyl vinyl ethers (as alkyl groups, for example, hexyl, octyl, decyl, ethylhexyl, methoxyethyl, ethoxyethyl, chloroethyl, 1-methyl-2,2-dimethylpropyl , 2-ethylbutyl, hydroxyethyl, hydroxyethoxyethyl, dimethylaminoethyl, diethylamino-ethyl, butylaminoethyl, benzyl and tetrahydrofurfuryl and vinyl aryl ethers (examples of aryl groups include For example, phenyl, tolyl, chlorophenyl, 2,4-dichloro-phenyl, naphthyl and anthranyl); Vinyl esters such as vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl-acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxy Acetate, vinyl phenylacetate, vinyl aceto-acetate, vinyl lactate, vinyl-b-phenylbutylate, vinyl cyclohexylcarboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate and vinyl Naphthoate; Styrene, for example styrene, alkyl styrene (e.g. methylstyrene, dimethylstyrene, trimethyl-styrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decyl-styrene, benzylstyrene , Chloromethylstyrene, trifluoromethylstyrene, ethoxymethylstyrene and acetoxymethylstyrene), alkoxystyrenes (eg methoxystyrene, 4-methoxy-3-methylstyrene and dimethoxystyrene) and halogenostyrene ( Examples: chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, penta-chlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4- Trifluoromethylstyrene and 4-fluoro-3-trifluoromethyl-styrene); Crotonates such as alkyl crotonates such as butyl crotonate, hexyl crotonate and glycerin monocrotonate; Dialkyl itaconates such as dimethyl itaconate, diethyl itaconate and dibutyl itaconate; Dialkyl maleates or fumarates such as dimethyl maleate and dibutyl fumarate; And (meth) acrylonitrile.
    [197] Hydroxystyrene homopolymers or copolymers or novolak-based phenolic resins such as poly (hydroxystyrene) and poly (hydroxystyrene-co-vinylcyclohexanol), novolak resins, cresol novolak resins and halogenated Phenol novolac resins may also be used. More specifically, for example, Japanese Patent Publications JP59-44615-B1 (the term "JP-B4" as used herein means Japanese Patent Publication), JP 54-34327-B4, and JP 58-12577-B4 and JP 54-25957-B4, JP 59-53836-A, JP 59-71048-A, JP 60-159743-A, JP 60-258539-A Methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acids described in JP 1-152449-A, JP 2-199403-A and JP 2-199404-A. Copolymers such as maleic anhydride copolymers with styrene comonomers, and maleic acid copolymers, and partially esterified maleic acid copolymers, which are described, for example, in US Pat. No. 5,650,263. Cellulose derivatives which can be further reacted with the amines described and also have carboxyl groups in the side chain can be used, for example, US Pat. No. 4,139,391, Japanese Patent Publication JP 59-44615 A copolymer of benzyl (meth) acrylate with (meth) acrylic acid, as described in -B4, JP 60-159743-A and JP 60-258539-A. Particular preference is given to copolymers with benzyl (meth) acrylate, (meth) acrylic acid and other monomers.
    [198] In polymers having carboxylic acid groups in the above organic binder polymer, several carboxylic acid groups react with glycidyl (meth) acrylate or epoxy (meth) acrylate, resulting in photosensitivity, coating film strength, coating solvent resistance and chemical resistance. And a photopolymerizable organic binder polymer for improving adhesion to a substrate can be obtained. Examples are described in JP 50-34443-B4; JP 50-34444-B4; US 5,153,095; T. Kudo et al., J. Appl. Phys., Vol. 37 (1998), p. 3594-3603; US 5,677,385; US 5,650,233.
    [199] Preferably, the organic polymer in the color filter resist composition comprises an alkali soluble copolymer comprising at least an unsaturated organic acid compound (eg acrylic acid, methacrylic acid, etc.) as the addition polymerization monomer unit. Alkali solubility, adhesive strength, chemical resistance, etc., using unsaturated organic acid ester compounds such as methyl acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, styrene and the like as further comonomers for polymer binders Can balance the characteristics of.
    [200] The organic polymer binder may be a tandem copolymer or block copolymer as described in US Pat. No. 5,368,976.
    [201] The weight average molecular weight of the binder is preferably 500 to 200,000, for example 2,000 to 150,000, more preferably 2,000 to 100,000.
    [202] These compounds may be used as a mono group or as a mixture of two or more kinds. The content of the binder in the photosensitive resin composition is preferably 10 to 95% by weight, more preferably 15 to 90% by weight based on the total solids.
    [203] Examples of color filter resists, compositions of such resists and processing conditions can be found in T. Kudo et al., Jpn. J. Appl. Phys. Vol. 37 (1998) 3594; T. Kudo et al., J. Photopolym. Sci. Technol. Vol 9 (1996) 109; K. Kobayashi, solid state Technol. Nov. 1992, p. S15-S18; US 5368976; US 5800952; US 5882843; US 5879855; US 5866298; US 5863678; JP 06-230212-A; EP 320264; JP 09-269410-A; JP 10-221843-A; JP 01-090516-A; JP 10-171119-A; US 5821016; US 5847015; US 5882843; US 5719008; EP 881541; EP 902327.
    [204] The photoinitiators of the present invention may be used, for example, in color filters such as those provided as examples above, or may replace some or all of the known photoinitiators in the resist. One skilled in the art will appreciate that the use of the photoinitiator of the present invention is not limited to formulations of specific binder resins, crosslinkers and color filter resists previously provided, but may be combined with dyes or color pigments or potential pigments to form radically polymerizable components. It is understood that it can be used in conjunction with to form photosensitive color filter inks or color filter resists.
    [205] The invention also relates to a color filter comprising the composition according to the invention.
    [206] Accordingly, the subject matter of the present invention also relates to red, green and blue elements (all of which include photosensitive resins and pigments comprising the multifunctional acrylate monomer, organic polymer binder and photopolymerization initiator) and, optionally, on a black matrix transparent substrate. And a color filter prepared by providing a transparent electrode to the surface of the substrate or the surface of the color filter layer. Suitable pigments as well as monomer and binder components are as described above. In the manufacture of the color filter, a transparent electrode layer can be applied on the surface of the transparent substrate or provided on the surface of the red, green and blue pixels and the black matrix. The transparent substrate is, for example, a glass substrate which may further have an electrode layer on its surface.
    [207] In order to improve the contrast of the color filter, it is desirable to apply a black matrix between color regions of different colors.
    [208] Instead of forming a black matrix using the photosensitive composition and patterning the black photosensitive composition by photolithography by patterned exposure (ie through a suitable mask) to form a black pattern that separates the red green and blue regions on the transparent substrate. Inorganic black matrices may also be used. These inorganic black matrices are photolithographic patterned by means of suitable imaging processes, for example, through etch resists, and after etching of the inorganic layer in areas not protected by etch resists, the remaining etch It may be formed from a metal (ie, chromium) film deposited on a transparent substrate using a process to remove the resist.
    [209] There are different known methods and steps by which black matrices can be applied in the color filter providing process. It may be applied directly on the transparent substrate before forming the above-mentioned red, green and blue filters, or may be applied after the red, green and blue pixels are formed on the substrate.
    [210] In different embodiments of color filters for liquid crystal displays, the black matrix can also be applied to the opposite substrate to the RGB color filter member containing substrate, which is separated from the opposite substrate by the liquid crystal layer, according to US Pat. No. 5,626,796.
    [211] As described in US Pat. No. 5,650,263, when a transparent electrode layer is attached after applying red, green and blue picturer members, and optionally a black matrix, an additional overcoat film as a protective layer is a color filter layer. Can be applied above.
    [212] For those skilled in the art, the photosensitive compositions of the present invention can be used to produce red, green and blue pixels, and black matrices for color filter manufacture regardless of the process differences, the additional layers and structures of the color filters that can be applied. Obvious. Forming colored pixels using the composition according to the invention will not be considered limited by the different structure and manufacturing process of such color filters.
    [213] In addition, in the color filter, the total solid component of each color may contain an ionic impurity-scavender, for example an organic compound having an epoxy group. The concentration of ionic impurity scavenger in the total solid component is generally in the range of 0.1 to 10% by weight.
    [214] Particularly in the above combinations of pigments and ionic impurity scavengers, examples of color filters are described in EP 320264. It is understood that the photoinitiators according to the invention can replace triazine initiator compounds in color filter formulations described in European Patent No. 320264.
    [215] The composition according to the present invention is a crosslinking agent activated by an acid, as described, for example, in JP 10 221843-A, and an acid is produced and crosslinked by heat or by actinic radiation. It may further comprise a compound that activates the binding reaction.
    [216] The compositions according to the invention may also comprise latent pigments containing photosensitive patterns or latent pigments which are transformed into finely dispersed pigments during thermal treatment of the coating. The heat treatment may be carried out after exposure or after development of the latent pigment containing photodegradable layer. Such latent pigments are soluble pigment precursors that can be transformed into insoluble pigments by, for example, the chemical, thermal, photolytic or radiation induced methods described in US Pat. No. 5,879,855. Modifications of these latent pigments can be improved upon exposure to actinic radiation or by addition of a compound that produces an acid by adding an acidic compound to the composition. Thus, color filter resists comprising latent pigments in the compositions according to the invention can also be produced.
    [217] The photosensitive composition of the present invention may be suitably used to form a color filter, but is not limited to the use.
    [218] The photosensitive compositions according to the invention can also be used to produce spacers that control the cell gap of the liquid crystal portion in the liquid crystal display panel. Since the properties of the light transmitted or reflected through the liquid crystal layer in the crystal display depend on the cell gap, thickness stability and uniformity over the pixel array are important variables for the performance of the liquid crystal display unit. In a liquid crystal cell, the spacing between the substrates in the cell is kept constant by interspersed glass or polymer spheres of about several micrometers in diameter as spacers between the substrates. Thus, spacers are held between the substrates to maintain the distance between the substrates at a constant value. The distance is determined by the diameter of the spacer. Spacers ensure minimum spacing between substrates. In other words, they prevent an increase in the distance between the substrates. However, they cannot prevent the substrates from being separated from each other, that is, they cannot prevent an increase in the distance between the substrates. In addition, the method using the spacer beads has a problem of uniformity of the diameter of the spacer beads, and the difficulty of uniform dispersion of the spacer beads on the panel, as well as the non-uniform orientation and position of the spacers on the pixel array region. There is a problem of reducing the brightness and / or optical aperture. Liquid crystal displays with large image display areas have recently attracted much attention. However, an increase in the area of the liquid crystal cell generally causes distortion of the substrate constituting the cell. The layer structure of the liquid crystal tends to be destroyed due to the deformation of the substrate. Thus, even when a spacer is used to keep the gap between the substrates constant, a liquid crystal display having a large image display area is not viable because the display is disturbed. Instead of the above spacer sphere dispersion method, a method of forming a column in the cell gap has been proposed. In this method, a resin column is formed as a spacer in the region between the pixel array region and the counter electrode to form a defined cell gap. Photosensitive materials having adhesive properties using photolithography are commonly used, for example, in the manufacturing process of color filters. The method is advantageous in that the position, number and height of the spacers can be freely adjusted as compared to conventional methods using spacer beads. In a color liquid crystal display panel, such spacers are formed in non-image areas under the black matrix of the color filter member. Therefore, the spacer formed using the photosensitive composition does not reduce the brightness and the optical cooking rate.
    [219] Photosensitive compositions for producing protective layers having spacers for color filters are described in JP 2000-81701-A, and a dry film type photoresist for spacer materials is also described in JP 11-A. 174459-A and JP 11-174464-A. As described in this document, the photosensitive composition, liquid and dry film photoresist comprises at least an alkali or acid soluble binder polymer, a radical polymerizable monomer and a radical initiator. In some cases, thermal crosslinkable components such as epoxides and carboxylic acids may further be included.
    [220] Forming a spacer using the photosensitive composition is as follows:
    [221] The photosensitive composition is applied to a substrate, such as a color filter panel, and the substrate is prebaked and then exposed to light through a mask. The substrate is then developed and patterned with a developer to form the desired spacers. If the composition contains some thermosetting components, postbaking is usually performed to thermally cure the composition.
    [222] The photocurable compositions according to the invention are suitable for producing spacers for liquid crystal displays (as described above) because of their high sensitivity.
    [223] The photosensitive composition according to the invention is also a reflective type comprising a liquid crystal display, more particularly an active matrix display having a thin film transistor (TFT) as a switching device and a passive matrix display without a switching device. It is suitable for making interlayer dielectric or dielectric layers in liquid crystal displays.
    [224] Recently, liquid crystal displays have been widely used, for example, for pocket TV sets and terminal devices for communication due to their small thickness and light weight. Reflective liquid crystal displays that do not require the use of a back light are required because they are particularly thin, lightweight and can significantly reduce power consumption. However, even if the halo is removed out of the currently available transmission color liquid crystal display and the light reflector is added to the lower surface of the display, there is a problem that the light utilization efficiency is low and cannot have practical brightness.
    [225] As a solution to this problem, various reflective liquid crystal displays have been proposed for improving the light utilization efficiency. For example, certain reflective liquid crystal displays have been devised that include pixel electrodes having a reflective function.
    [226] Reflective liquid crystal displays include an insulating substrate and an opposing substrate spaced apart from the insulating substrate. The space between the substrates is filled with liquid crystal. A gate electrode is formed over the insulating substrate, and both the gate electrode and the insulating substrate are covered with the gate insulating film. Subsequently, a semiconductor layer is formed over the gate insulating film on the gate electrode. A source electrode and a drain electrode are also formed on the gate insulating film in contact with the semiconductor layer. The source electrode, the drain electrode, the semiconductor layer and the gate electrode cooperate with each other to form a lower gate type TFT as a switching device.
    [227] An interlayer insulating film covering the source electrode, the drain electrode, the semiconductor layer, and the gate insulating film is formed. A contact hole is formed through the interlayer insulating film on the drain electrode. A pixel electrode made of aluminum is formed on both the interlayer insulating film and the inner sidewall of the contact hole. The drain electrode of the TFT is eventually in contact with the pixel electrode through the interlayer insulating film. Interlayer insulating layers are generally designed such that the pixel electrode has a roughened surface that acts as a reflector to diffuse light to obtain a wider viewing angle (visibility).
    [228] Reflective liquid crystal displays significantly improve the light utilization efficiency by the advantage that the pixel electrode acts as a light reflector.
    [229] In the above-mentioned reflective liquid crystal display, the interlayer insulating film is designed to have protrusions and depressions by photolithography. In order to form and control finely shaped protrusions and depressions (µm) for surface roughness and to form contact holes, a photolithography method using a positive photoresist and a negative photoresist is used. The composition according to the invention is particularly suitable for these resists.
    [230] The photosensitive compositions according to the invention are also suitable for producing microlens arrays for use in liquid crystal display panels, image sensors and the like.
    [231] Microlenses are microscopic passive optical components that are mounted on active optoelectronic devices such as detectors, displays, and light emitting devices (light emitting diodes, transversal and termination cavity lasers) to improve their input or output quality. The field of application is wide and covers such areas as telecommunications, information technology, audio-visual services, solar cells, detectors, solid state light sources and optical communication networks.
    [232] Current optical systems use a variety of techniques to efficiently combine microlenses and microoptical devices.
    [233] The microlens array is a line image sensor used in, for example, a facsimile or the like, for concentrating incident light, for concentrating illumination of a display by focusing light on a pixel area of a non-luminous display device, for example, a liquid crystal display device. As a means of forming an image in the photoelectric conversion region of a line image sensor to improve the sensitivity of these devices, it is used to form an image to be printed on photosensitive means used in a liquid crystal printer or a light emitting diode (LED) printer.
    [234] The most common use is for increasing the efficiency of photodetector arrays in solid state image sensing devices such as charge coupled devices (CCDs). In the detector array, it is desired to collect as much light as possible for each detector element or pixel. When a microlens is placed on top of each pixel, the lens collects incident light and concentrates it on an active area smaller than the size of the lens.
    [235] According to the prior art, microlens arrays can be manufactured in various ways:
    [236] (1) After the pattern of the plate-shaped lens is drawn on the thermoplastic resin by ordinary photolithography or the like, settlement occurs at the pattern edge by heating the thermoplastic lens to a temperature higher than the softening point of the lens to make it fluid (so-called). "Reflow") to obtain a convex lens (JP 60-38989-A, JP 60-165623-A, JP 61-67003-A and JP 2000-39503-A). In this method, when the thermoplastic resin used is photosensitive, the pattern of the lens can be obtained by exposing the lens to light.
    [237] (2) When the photosensitive resin is exposed to light in a desired pattern using an aligner, the unreacted monomer moves from an unexposed area to an exposed area, causing swelling of the exposed area. Method of forming a convex lens based on [Ref. Journal of the Research Group in Microoptics Japanese Society of Applied Physics, Colloquium in Oprics, Vol. 5, No. 2, pp. 118-123 (1987) and Vol. 6, No. 2, 00. 87-92 (1988).
    [238] A photosensitive resin layer is formed on the upper surface of the support substrate. Then, using a separate shielding mask, the upper surface of the photosensitive resin layer is irradiated with light from a mercury lamp or the like to expose the photosensitive resin layer to light. As a result, the exposed portion of the photosensitive resin layer swells in the form of a double-green lens to form a light concentrating layer having a plurality of microlenses.
    [239] (3) Obtaining a convex lens in which the photo edge is exposed to light by a close exposure technique in which the photomask is not in contact with the resin to blur the pattern edge, so that the amount of the photochemical reaction product is distributed according to the blurring at the pattern edge. Method [cf. JP 61-153602-A].
    [240] (4) A method of generating a lens effect in which a photosensitive resin is exposed to light having a specific intensity distribution to form a refractive index distribution pattern in accordance with the light intensity (JP 60-72927-A and JP 60-166946-A).
    [241] The photosensitive composition according to the present invention can be used in any of the above methods to form a microlens array using the photocurable resin composition.
    [242] A particular class of techniques is focused on forming microlenses in thermoplastic resinous photoresists. Examples are described in Popovic et al., In the reference SPIE 898, pp. 23-25 (1988). A technique called reflow technology is to define a footprint of a lens on a thermoplastic resin, for example, by photolithography on a photosensitive resin such as a photoresist, and then heating the material above its reflow temperature. It includes. Surface tension draws the island of photoresist into a spherical cap of the same volume as the initial island before reflow. The cap is a flat convex microlens. Advantages of the art are, among others, simplicity, reproducibility, and the possibility of integrating directly on top of luminescent or photodetecting optoelectronic devices.
    [243] In some cases, an overcoat layer is formed on the rectangular pantonized lens unit prior to reflow to prevent the island of resin from settling in the middle without reflowing into the spherical cap in the reflow step. The overcoat acts as a permanent protective layer. The coating layer is also made of the photosensitive composition.
    [244] The active energy ray curable composition used to form the lens zone must have various properties, including adhesion to the transparent substrate, and have suitable optical properties.
    [245] Lenses having at least several photoresists in the prior art are undesirable for some applications because of poor light transmission at the blue end of the optical spectrum.
    [246] Since the photocurable compositions according to the invention have low yellowing properties thermally and photochemically, they are suitable for producing such microlens arrays.
    [247] The novel radiation-sensitive composition is suitable for the photolithography step used in the manufacturing process of plasma display panels (PDPs), in particular for the image forming process of barrier ribs, phosphor layers and electrodes.
    [248] PDPs are flat displays that display images and information due to the emission of light by gas discharge. By the configuration of the panel and the method of operation, it is known in two types: DC (direct current) type and AC (AC) type.
    [249] As an example, the principle of the DC type color PDP is briefly described. In the DC type color PDP, the space interposed between two transparent substrates (generally glass plates) is divided into a plurality of fine cells by lattice barrier ribs inserted between the transparent substrates. Each cell is sealed with a discharge gas such as He or Xe. On the rear wall of each cell there is a phosphor layer that emits three primary colors of visible light when excited by the ultraviolet light generated by the discharge of the discharge gas. On the inner surface of the two substrates the electrodes are positioned opposite each other across the relevant cell. Generally, the cathode is formed from a film of transparent electroconductive material such as NESA glass. When a high voltage is applied between these electrodes formed in the front wall and the back wall, the discharge gas sealed in the cell causes a plasma discharge, resulting in red, blue and green fluorescence due to the emitted ultraviolet light. The element is stimulated to emit light and to display an image. In a full color display system, three fluorescent elements each of the three primary colors red, blue and green mentioned above together form one pixel.
    [250] The cells in the DC type PDP are distinguished by the component barrier ribs of the lattice, while the cells in the AC type PDP are distinguished by the barrier ribs arranged in parallel with each other on the surface of the substrate. In either case, the cells are separated by barrier ribs. These barrier ribs are intended to limit luminescent discharges within a fixed area to prevent erroneous discharges or crosstalk between adjacent discharge cells and to ensure an ideal display.
    [251] The composition according to the invention can be used for the production of one or more materials for image recording or image reproduction, which can be monochromatic or multicolored. The material is also suitable for color processing systems. In this technique, formulations containing microcapsules can be used and heat treated after radiation curing for image generation. Such systems and techniques and their use are described, for example, in US Pat. No. 5,359,593.
    [252] The compositions of the present invention are also suitable for photopatternable compositions for forming dielectric layers of multilayer circuit boards produced by sequential accumulation processes and for photopatternable compositions for solder mask generation.
    [253] The invention therefore also relates to a photoresist comprising the composition according to the invention.
    [254] Accordingly, the subject of the present invention is also a solder resist comprising the composition.
    [255] An image forming process, for example a solder mask manufacturing process
    [256] (1) mixing the components of the composition,
    [257] (2) apply the resulting composition to a substrate (" cover " of the substrate);
    [258] (3) when present, the solvent is evaporated at an elevated temperature, for example at a temperature of from 80 to 90 ° C,
    [259] (4) the coated substrate is concentrated in the electromagnetic radiation through the negative mask (this initiates the reaction of the acrylate),
    [260] (5) the irradiated sample was developed by washing with an aqueous alkali solution to remove uncured areas,
    [261] (6) heat curing the sample, for example at about 150 ° C. to initiate crosslinking between the carboxylic acid and the epoxy component.
    [262] The method of the present invention is another object of the present invention.
    [263] Still another object of the present invention is a method of photopolymerization of an ethylenically unsaturated double bond containing compound comprising irradiating the composition with an electromagnetic radiation or an electron beam or X-ray of 190 to 600 nm.
    [264] Still another object of the present invention is to color or uncolored paints and varnishes, powder coatings, optical fiber coatings, printing inks, printing plates, adhesives, dental compositions, photoresists for electronic devices such as electroplating resists, etch Both resists, electroluminescent displays and LCDs, color filter materials, for the production of color filters for various display articles or for the production of plasma-display panels for the production of solder resists, both for resists, for liquid and anhydrous films. As a composite composition, for the manufacture of compositions for encapsulating electrical and electronic components, magnetic recording materials, microengineered components, waveguides, optical switches, plating masks, etch masks, color processing systems, glass fiber cable coatings, screen printing stencils, In order to produce three-dimensional objects via stereolithography, in particular image recording materials for holographic recording, As a bleaching material for microelectronic circuits, bleaching materials, image recording materials, for image recording materials using microcapsules, as a photoresist material for UV and visible light laser direct image systems, and in a sequential accumulation layer of a printed circuit board It is not only a use as a photoresist material used to form a film, but also a method for preparing the material.
    [265] Still another object of the present invention is a method for producing a photograph of a coated substrate and a relief image having one or more surfaces coated with the composition of the present invention, wherein the unexposed portion after imagewise exposure of the coated substrate. Remove with a developer.
    [266] The following examples illustrate the invention more similarly. Detailed Description The remainder and parts and percentages in the claims are by weight unless otherwise indicated. When an alkyl radical having 3 or more carbon atoms is described without mention of specific isomers, it means in each case n-isomers.
    [267] The following photoinitiators are used in the examples.
    [268]
    [269]
    [270]
    [271]
    [272] Example 1 Preparation of Poly (benzylmethacrylate-co-methacrylic acid)
    [273] 24 g of benzyl methacrylate, 6 g of methacrylic acid and 0.525 g of azobisisobutyronitrile (AIBN) are dissolved in 90 ml of propylene glycol 1-monomethyl ether 2-acetate (PGMEA). The resulting reaction mixture is placed in a preheated 80 ° C. oil bath. After stirring under nitrogen at 80 ° C. for 5 hours, the resulting viscous solution is cooled to room temperature and used without further purification. Solids content is about 25%. The weight ratio of benzyl methacrylate: methacrylic acid is 80:20.
    [274] Example 2: Developability test in red resist
    [275] 160.0 parts by weight of a copolymer of benzyl methacrylate and methacrylic acid according to Example 1
    [276] Dipentaerythritol hexaacrylate (DPHA, manufactured by UCB Chemicals) 40.0 parts by weight
    [277] IRGAPHOR RED BT-CF (Red Pigment, Ciba Specialty Chemicals) 40.0 parts by weight
    [278] PGMEA 360.0 parts by weight
    [279] The components are mixed and dispersed using a Paint conditioner (SKANDEX) to produce a red resist dispersion. To the dispersion is added the photoinitiator to be tested. The prepared color resist is applied to an aluminum substrate with an electric applicator equipped with a wire wound bar. The applied substrate is dried at 80 ° C. for 10 minutes. The thickness of the dry film is approximately 2 μm. The resist is developed with a 1% aqueous solution of sodium carbonate at 30 ° C. using a spray developer (Walter Lemmen, model T21). The development time, which is the time for completely removing the resist layer by development, is measured. Lower values are more suitable formulations. The photoinitiators used and the results are listed in Table 1.
    [280] Development time of red resist PhotoinitiatorConcentration [art by weight]Developing time [sec] none-80 (1) (1)2.46.0115115 (2) (2)2.46.0115120 (3) (3)2.46.09090 (4) (4)2.46.095100
    [281] Example 3: Sensitivity Test
    [282] A photocurable formulation is prepared by mixing the following ingredients:
    [283] 100.0 parts by weight of acrylated acrylic copolymer (ACA200M, manufactured by Daicel Industries, Ltd., solid content is 50% by weight),
    [284] 7.5 parts by weight of dipentaerythritol hexaacrylate (DPHA, manufactured by UCB Chemicals),
    [285] PGMEA 50.0 parts by weight and
    [286] Photoinitiators to be tested in the amounts given in Table 2.
    [287] The photoinitiator to be tested is added to the above formulation and mixed. The composition is applied to an aluminum plate using an electric applicator with a wire wound bar. Removal is by heating at 80 ° C. for 15 minutes in a convection oven. The thickness of the dry film is approximately 5 μm. An acetate film is applied to the coating and a standardized test negative film having 21 different step density of the step (Stouffer step wedge) is placed thereon. The sample is applied with another UV-transparent film and pressed over the metal via a vacuum. Place the interference filter on top to select wavelength 405nm. Exposure is made using a 250 W ultra-high pressure mercury lamp (USHIO, USH-250BY) at a distance of 15 cm. The total exposure capacity measured by the test negative film optical power meter (OCR UV light meter model UV-M02 with UV-42 detector) is 4000 mJ / cm 2 . After exposure, the exposed film is developed with an aqueous 1% sodium carbonate solution at 30 ° C. for 1 minute using a spray developer (Walter Lemmen, model T21). The sensitivity of the initiator system used is characterized by indicating the highest number of remaining (ie polymerized) steps after development. The greater the number of steps, the greater the sensitivity of the system tested. Photoinitiators and test results are shown in Table 2.
    [288] Sensitivity test results PhotoinitiatorConcentration [art by weight]Number of post-exposure steps of 4000 J / cm 2(2) (2) (2) (2)7.511.015.020.03557 (4) (4) (4) (4)7.511.015.020.03556
    权利要求:
    Claims (17)
    [1" claim-type="Currently amended] Oligomers or polymers (A) containing at least one carboxylic acid group in a molecule and having a molecular weight of 200,000 or less,
    At least one photoinitiator compound of formula (B) and
    A photosensitive composition comprising a monomeric, oligomeric or polymeric compound (C) having at least one olefinic double bond.
    Formula I

    In Formula I above,
    R 1 is straight or branched C 1 -C 12 alkyl,
    R 2 is straight or branched C 1 -C 4 alkyl,
    R 3 and R 4 independently of one another are straight or branched C 1 -C 8 alkyl.
    [2" claim-type="Currently amended] 2. The photoinitiator compound according to claim 1, wherein the photoinitiator compound is R 1 is straight or branched C 1 -C 4 alkyl, R 2 is methyl, ethyl or propyl, especially ethyl and R 3 and R 4 are independently of each other straight or branched C 1- A photosensitive composition which is a compound of formula (I) which is C 4 alkyl, especially methyl.
    [3" claim-type="Currently amended] The compound of claim 1, wherein the compound of formula I is 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-methylbenzyl) -butan-1-one, 1- [4-morpholino Phenyl] -2-dimethylamino-2- (4-ethylbenzyl) -butan-1-one, 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-isopropylbenzyl) -butane -1-one, 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-n-propylbenzyl) -butan-1-one, 1- [4-morpholinophenyl] -2 -Dimethylamino-2- [4- (2-methylprop-1-yl) -benzyl] -butan-1-one, 1- [4-morpholinophenyl] -2-dimethylamino-2- (4 -n-butylbenzyl) -butan-1-one, in particular 1- [4-morpholinophenyl] -2-dimethylamino-2- (4-methylbenzyl) -butan-1-one.
    [4" claim-type="Currently amended] The photosensitive composition according to claim 1, wherein the component (A) has a molecular weight of 2,000 to 150,000.
    [5" claim-type="Currently amended] The process according to claim 1, in addition to components (A), (B) and (C), at least one photosensitizer compound (E), in particular benzophenone and its derivatives, thioxanthone and its derivatives, anthraquinone and its A photosensitive composition comprising a derivative and a compound selected from the group consisting of coumarins and derivatives thereof.
    [6" claim-type="Currently amended] 2. The at least one compound according to claim 1, in addition to components (A), (B) and (C), and at least one compound having an epoxy group as the thermosetting component (F), preferably one epoxy curing accelerator (G2). Photosensitive composition comprising a.
    [7" claim-type="Currently amended] The photosensitive composition of claim 1 comprising at least one UV absorber or light stabilizer compound (G3) in addition to components (A), (B) and (C).
    [8" claim-type="Currently amended] The photosensitive composition according to claim 1, comprising an additive (G) selected from the group consisting of inorganic fillers, colorants, dispersants, thermal polymerization initiators, thickeners, antifoaming agents and leveling agents, in particular inorganic fillers.
    [9" claim-type="Currently amended] The photosensitive composition according to claim 1, comprising 0.015 to 100 parts by weight, preferably 0.03 to 80 parts by weight of photoinitiator (B), based on 100 parts by weight of component (A).
    [10" claim-type="Currently amended] A method of photopolymerization of an ethylenically unsaturated double bond containing compound, comprising irradiating the composition according to any one of claims 1 to 9 with electromagnetic radiation, electron beams or X-rays in the range of 190 to 600 nm.
    [11" claim-type="Currently amended] Colored and uncolored paints and varnishes, powder coatings, optical fiber coatings, printing inks, printing plates, adhesives, dental compositions, optical resists for electronic devices such as electroplating resists, etch resists, Both liquid and anhydrous films, as resists for the production of solder resists, for the production of color filters for various display articles or for the production of structures in the manufacturing of plasma-display panels, electroluminescent displays and LCDs, color filter materials, composite compositions, And compositions for encapsulating electronic components, magnetic recording materials, microengineered components, waveguides, optical switches, plating masks, etch masks, color processing systems, glass fiber cable coatings, for screen printed stencil manufacturing, three-dimensional through steoliolithography Image recording materials, microelectronic circuits, bleaching materials, image recording materials for the production of objects, in particular for holographic recording Photoresist material used for forming a dielectric layer in a sequential accumulation layer of a printed circuit board and as a photochromic material for a photochromic material, for an image recording material using microcapsules, for UV and visible light laser direct imaging systems Use of the photosensitive composition according to any one of claims 1 to 9 as a.
    [12" claim-type="Currently amended] The photoresist according to claim 10, which is colored or uncolored paints and varnishes, powder coatings, optical fiber coatings, printing inks, printing plates, adhesives, dental compositions, electroplating resists for electroplating resists, etch resists, liquids And both anhydrous films, resist resists for the production of solder resists, for the production of color filters for various display articles or for the manufacture of plasma-display panels, for the production of electroluminescent displays and LCDs, composite compositions, color filter materials, electrical And compositions for electronic component encapsulation, magnetic recording materials, microelectronic components, waveguides, optical switches, plating masks, etch masks, color processing systems, fiberglass cable coatings, screen printing stencil manufacturing, microlithography, plating and photoforming methods Production of three-dimensional objects, in particular image recording materials for holographic recording, microelectronic circuits, Materials, bleaching materials for image recording materials, bleaching materials for image recording materials using microcapsules, formation of dielectric layers in sequential accumulation layers of printed circuit boards, and UV and visible light lasers as direct light sources of imaging technology Method for making process.
    [13" claim-type="Currently amended] A coated substrate, wherein the composition according to claim 1 is coated on at least one surface.
    [14" claim-type="Currently amended] A method of manufacturing a photolithography of a relief image, wherein after the imagewise exposure of the coated substrate according to claim 13, the unexposed portion is removed with a developer.
    [15" claim-type="Currently amended] A photoresist comprising the composition of claim 1.
    [16" claim-type="Currently amended] Color filter resist comprising the composition of claim 1.
    [17" claim-type="Currently amended] A color filter prepared by providing red, green and blue pixels and a black matrix (all of which include photosensitive resins and pigments) on a transparent substrate and providing transparent electrodes on the surface of the substrate or on the surface of the color filter layer. Color resin, characterized in that the resin comprises a polyfunctional acrylate monomer, an organic polymer binder and a photopolymerization initiator of formula (I) as defined in claim 1.
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    同族专利:
    公开号 | 公开日
    WO2003010602A8|2003-08-07|
    CN1547683A|2004-11-17|
    ES2375471T3|2012-03-01|
    CN1327293C|2007-07-18|
    AT530951T|2011-11-15|
    EP1410109A1|2004-04-21|
    US20040192804A1|2004-09-30|
    US20070249748A1|2007-10-25|
    US7556843B2|2009-07-07|
    EP1410109B1|2011-10-26|
    WO2003010602A1|2003-02-06|
    US7247659B2|2007-07-24|
    US20070259278A1|2007-11-08|
    JP2004536352A|2004-12-02|
    CA2453237A1|2003-02-06|
    KR100908795B1|2009-07-22|
    US7425585B2|2008-09-16|
    JP4312598B2|2009-08-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-07-26|Priority to EP01810734.2
    2001-07-26|Priority to EP01810734
    2002-07-18|Application filed by 시바 스페셜티 케미칼스 홀딩 인크.
    2002-07-18|Priority to PCT/EP2002/007989
    2004-04-09|Publication of KR20040030848A
    2009-07-22|Application granted
    2009-07-22|Publication of KR100908795B1
    优先权:
    申请号 | 申请日 | 专利标题
    EP01810734.2|2001-07-26|
    EP01810734|2001-07-26|
    PCT/EP2002/007989|WO2003010602A1|2001-07-26|2002-07-18|Photosensitive resin composition|
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