JP6093766B2 - Photopolymerizable unsaturated resin, photosensitive resin composition containing the same, and light shielding spacer and liquid crystal display device formed therefrom - Google Patents

Description

  The present invention relates to a novel photopolymerizable unsaturated resin, a photosensitive resin composition containing the same, and a light shielding spacer and a liquid crystal display device formed therefrom.

  A liquid crystal display (LCD) device, which is a type of flat panel display device that is currently widely used, has a thin film transistor (TFT) substrate on which pixel electrodes are formed, and a common electrode formed on the thin film transistor (TFT) substrate. And a color filter substrate facing the TFT substrate, and a liquid crystal layer inserted between the TFT substrate and the color filter substrate. Such LCD devices display images in a manner that controls the amount of light transmitted through the liquid crystal layer by applying a voltage to the pixel electrode and the common electrode and rearranging the liquid crystal molecules in the liquid crystal layer.

  As consumption patterns have become more diverse, there has been a need for a display that maximizes space utilization and is easily portable by having low power consumption, light weight and thin thickness, and high screen quality. Thus, various attempts have been made to further reduce the thickness of the display. As one attempt, techniques have been suggested for forming a color filter layer directly in a TFT structure, instead of the conventional technique of separately manufacturing a TFT lower substrate and a colored upper substrate and then laminating the substrates. It was.

  In a new technique for forming a color filter layer directly in a TFT structure, the spacer is generally formed from a photosensitive composition by using lithography. In order to prevent the malfunction of the TFT as a switching device caused by incident light, this spacer should have light shielding properties. In order to manufacture such a light shielding spacer, it has been suggested that carbon black is mixed with the photosensitive resin composition. However, when manufacturing a spacer from a photosensitive resin composition containing carbon black, the electric field applied to the upper and lower substrates causes an electrical distortion phenomenon due to the high dielectric constant of carbon black. is there. Thus, there is a need to develop spacers with excellent light hiding properties and low dielectric constants.

  Furthermore, the photosensitive resin composition used in the manufacture of the light shielding spacer is generally a black composition prepared by mixing dyes having various colors or various kinds of dyes. Does not dissolve easily in developer. Due to the low solubility in the developer, these dyes have the problem of poor development properties, requiring a long time for development, or failing to obtain the desired degree of resolution. In particular, the importance of resolution is further increased when forming colored independent dot spacer patterns.

  Further, since there should be a height difference between the main spacer and the sub-spacer in the spacer, the height of the completed spacer according to the arrangement should be a certain ratio, and that spacer is the upper substrate In order to maintain resistance to the above pressure, the exposure energy should be controlled because it should also have some physical properties such as elastic recovery.

  Korean Patent Application Publication No. 2010-0066197 has a good patterning property, and shows a high compressive displacement and a high recovery rate when a thin film is formed, and a low dielectric constant and an excellent optical density. A black photosensitive resin composition is disclosed. However, this document does not consider the resolution of thin films formed from this composition and considers a recovery rate of 70% as appropriate, which is the level of recovery rate required by the relevant industry. Not satisfied.

  JP 2002-040440 discloses a radiation sensitive composition, which can form a spacer with excellent light shielding properties and high mechanical strength and heat resistance, and this composition can be used during panel sealing. The composition does not irreversibly deform and the composition does not cause display defects due to gap differences in the liquid crystal layer. However, this document does not consider the dielectric constant or resolution in the spacer formed from this composition.

Korean Patent Application Publication No. 2010-0066197 JP 2002-040440 A

  1st aspect of this invention provides the photopolymerizable unsaturated resin of the novel structure which should be contained in the photosensitive resin composition.

  The second aspect of the present invention comprises a novel photopolymerizable unsaturated resin and forms a dot spacer pattern with a size of 10-100 μm due to sufficient solubility in the developer before and after exposure. And a photosensitive resin composition capable of maintaining excellent light shielding properties while reducing the dielectric constant of the formed dot spacer pattern.

  The third aspect of the present invention provides a light shielding spacer formed from a photosensitive resin composition and having sufficient resolution and excellent elastic recovery rate.

  A fourth aspect of the present invention provides a liquid crystal display device having a light shielding spacer.

According to one embodiment of the present invention, the epoxy resin (A) represented by formula I is reacted with an unsaturated basic acid (B) to form an epoxy adduct (AB), and the adduct is It is a product (P1) obtained by reacting with a basic acid anhydride (C), or an epoxy resin (A) represented by the formula I is reacted with an unsaturated basic acid (B) to form an epoxy. An adduct (AB) is formed, the adduct is reacted with polybasic anhydride (C) to form product (P1), and the product (P1) is further converted to monofunctional or polyfunctional There is provided a photopolymerizable unsaturated resin which is a product (P2) obtained by reacting with a functional epoxy compound (D).

からなる群から選択される１つにおける^＊で標識された炭素で置き換えられ、
Ｌ^１はＣ_１−１０アルキレン、Ｃ_３−２０シクロアルキレンまたはＣ_１−１０アルキレンオキシであり、
Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６およびＲ^７は同じかまたは異なっており、かつそれぞれ独立して、水素、Ｃ_１−１０アルキル、Ｃ_１−１０アルコキシ、Ｃ_２−１０アルケニルおよびＣ_６−１４アリールからなる群から選択され、
Ｒ^８は水素、ハロゲン若しくはヒドロキシで置換されているかもしくは置換されていないＣ_１−１０アルキル、Ｃ_２−１０アルケニルおよびＣ_６−１４アリールからなる群から選択され、並びに
ｎは０〜１０の整数である。 In the formula, carbon labeled with ^*

Replaced with carbon labeled with ^* in one selected from the group consisting of ^:
L ¹ is C _1-10 alkylene, C _3-20 cycloalkylene or C _1-10 alkyleneoxy,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, C ₂ Selected from the group consisting of _-10 alkenyl and C _6-14 aryl;
R ⁸ is selected from the group consisting of hydrogen, halogen or hydroxy substituted or unsubstituted C _1-10 alkyl, C _2-10 alkenyl and C _6-14 aryl, and n is an integer from 0 to 10 It is.

According to another aspect of the present invention, there is provided a photosensitive resin composition comprising a photopolymerizable unsaturated resin, a functional monomer having at least one ethylenically unsaturated bond, a polymerization initiator, a black organic pigment, and a solvent. .
According to a further aspect of the present invention, there is provided a light shielding spacer formed from a photosensitive resin composition.
According to yet a further aspect of the invention, a liquid crystal display device having a spacer is provided.

  The photosensitive resin composition comprising the photopolymerizable unsaturated resin according to the present invention has a light shielding having a dot spacer pattern with a size of 10 to 100 μm due to sufficient solubility in a developer before or after exposure. Spacers can be formed. Furthermore, the formed light shielding spacer has a low dielectric constant of 8 or less, and has an optical density of 1.0 or more per μm, so that it has excellent light shielding properties, and sufficient resolution and excellent elasticity. Has a recovery rate.

  Hereinafter, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention.

1. Photopolymerizable unsaturated resin
The photopolymerizable unsaturated resin is obtained by reacting the epoxy resin (A) represented by the formula I with an unsaturated basic acid (B) to form an epoxy adduct (AB). The product (P1) obtained by reacting with the basic acid anhydride (C), or by further reacting the monofunctional or polyfunctional epoxy compound (D) with the product (P1) This is the product (P2) obtained.

Epoxy adduct (AB) is 0.1 to 5 equivalents, preferably 0.2 to 2 equivalents, and more preferably 0, of epoxy resin (A) corresponding to 1 equivalent of epoxy groups, according to known addition reactions. It can be obtained by reacting with an unsaturated basic acid (B) corresponding to 4 to 1 equivalent of a carboxyl group.

The photopolymerizable unsaturated resin contains 0.1 to 5 equivalents, preferably 0.2 to 2 equivalents, and more preferably 0.4 to 1 equivalents of an epoxy adduct (AB) corresponding to 1 equivalent of a hydroxyl group. This is a product (P1) obtained by reacting with a polybasic acid anhydride (C) corresponding to an acid anhydride group. The photopolymerizable unsaturated resin can be obtained by reacting the epoxy adduct (AB) with the polybasic acid anhydride (C) according to a known esterification reaction.

  Furthermore, the photopolymerizable unsaturated resin is used in an amount of 0.1 to 5 equivalents in the monofunctional or polyfunctional epoxy compound, preferably 0.2 to 1 equivalent to 1 equivalent of the hydroxyl group of the epoxy adduct (AB). Monofunctional or polyfunctional epoxy compounds (D) can be obtained by further esterification with product (P1) in an amount of epoxy groups of 2 equivalents, and more preferably 0.3-1 equivalents.

Esterification between the product (P1) obtained by esterifying the epoxy adduct (AB) with a polybasic acid anhydride (C) and the monofunctional or polyfunctional epoxy compound (D) is: It can occur between the carboxyl group resulting from the polybasic acid anhydride (C) and the epoxy group of the monofunctional or polyfunctional epoxy compound (D).

Furthermore, in order to efficiently advance the reaction between the carboxyl group generated from the polybasic acid anhydride (C) and the epoxy group of the monofunctional or polyfunctional epoxy compound (D), a photopolymerizable unsaturated resin is used. (I) an epoxy adduct (AB) corresponding to 1 equivalent of a hydroxyl group, an acid anhydride equivalent of a polybasic acid anhydride (C) and an epoxy equivalent of a monofunctional or polyfunctional epoxy compound (D) Reacting with an amount of polybasic acid anhydride (C) in an amount such that the total amount is 1.0 equivalent or more, preferably 1.1 to 2.0 equivalents, and (ii) the product Can be prepared by further reacting with a monofunctional or polyfunctional epoxy compound (D).

  The photopolymerizable unsaturated binder resin preferably has a weight average molecular weight (Mw) in the range of 1,500 to 20,000, more preferably 3,000 to 15,000. If the weight average molecular weight of the photopolymerizable unsaturated resin is within the above range, the fluidity of the resin is maintained within an appropriate range, and thus the handling characteristics and pattern formability are good.

  The photosensitive resin composition according to the present invention may contain 0.5 to 50% by weight of a photopolymerizable unsaturated binder resin with respect to the total weight of the photosensitive resin composition other than the remaining solvent amount. If the content of the photopolymerizable unsaturated binder resin is within the above range, the pattern is easily formed after the exposure and development processes, the basic physical characteristics of the light shielding material are satisfactory, the processing time, For example, development time and sensitivity are optimized, and properties such as compression properties, chemical resistance, etc. are improved.

(A) Epoxy resin The epoxy resin (A) used in the present invention is a compound represented by the following formula 1 having a 9H-xanthene skeleton.

  The 9H-xanthene skeleton structure of the epoxy resin (A) improves the adhesion between the cured product and the substrate, alkali resistance, formability, strength, etc., and develops and removes the uncured part when removing the uncured part. It functions as a factor that increases the resolution of the pattern.

からなる群から選択される１つにおける^＊で標識された炭素で置き換えられ、
Ｌ^１はＣ_１−１０アルキレン基、Ｃ_３−２０シクロアルキレン基またはＣ_１−１０アルキレンオキシ基であり、
Ｒ^１〜Ｒ^７は互いに同じかまたは異なっており、かつそれぞれ独立して、水素原子、Ｃ_１−１０アルキル基、Ｃ_１−１０アルコキシ基、Ｃ_２−１０アルケニル基またはＣ_６−１４アリール基であり、
Ｒ^８は水素原子、エチル基、ＣＨ_３ＣＨＣｌ−、ＣＨ_３ＣＨＯＨ−、ＣＨ_２＝ＣＨＣＨ_２−およびフェニル基からなる群から選択され、並びに
ｎは０〜１０の整数である。 In the formula, carbon labeled with ^*

Replaced with carbon labeled with ^* in one selected from the group consisting of ^:
L ¹ is a C _1-10 alkylene group, a C _3-20 cycloalkylene group or a C _1-10 alkyleneoxy group,
R ^{1 to} R ⁷ are the same as or different from each other, and each independently represents a hydrogen atom, a C _1-10 alkyl group, a C _1-10 alkoxy group, a C _2-10 alkenyl group or a C _6-14 aryl group. And
R ⁸ is a hydrogen atom, an ethyl _{group, CH 3 CHCl-, CH 3 CHOH-} , CH 2 = CHCH 2 - is selected from the group consisting of and phenyl group, and n is an integer of 0.

Specific examples of the C _1-10 alkylene group include methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, isopentylene group, tert-pentylene. A hexylene group, a heptylene group, an octylene group, an isooctylene group, a tert-octylene group, a 2-ethylhexylene group, a nonylene group, an isononylene group, a decylene group, and an isodecylene group.

Specific examples of the C _3-20 cycloalkylene group may include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a decalinylene group, and an adamantylene group.

Specific examples of the C _1-10 alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a sec-butyleneoxy group, a tert-butyleneoxy group, a pentyleneoxy group, and a hexyleneoxy group. , Heptyleneoxy groups, octyleneoxy groups, and 2-ethyl-hexyleneoxy groups.

Specific examples of the C _1-10 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a tert-pentyl group. Hexyl group, heptyl group, octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, and isodecyl group.

Specific examples of C _1-10 alkoxy groups include methoxy, ethoxy, propyloxy, butyloxy, sec-butoxy, tert-butoxy, pentoxy, hexyloxy, heptoxy, octyloxy, and A 2-ethyl-hexyloxy group may be mentioned.

Specific examples of C _2-10 alkenyl groups may include vinyl, allyl, butenyl, and propenyl groups.

Specific examples of the C _6-14 aryl group may include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

(B) Unsaturated basic acid Unsaturated basic acid (B) used in this invention is used in order to improve the sensitivity of the photosensitive resin composition containing a photopolymerizable unsaturated resin according to this invention. Specific examples of the unsaturated basic acid (B) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate-maleate, hydroxyethyl acrylate-maleate, hydroxypropyl methacrylate-maleate, hydroxy Propyl acrylate-maleate, dicyclopentadiene-maleate, and polyfunctional (meth) acrylates having a carboxyl group and two or more (meth) acryloyl groups may be mentioned, but are not limited thereto. This unsaturated basic acid may be used alone or in combination of two or more thereof. Acrylic acid, methacrylic acid and polyfunctional (meth) acrylates having carboxyl groups and two or more (meth) acryloyl groups are preferably used as unsaturated basic acids.

  The polyfunctional (meth) acrylate having a carboxyl group and two or more (meth) acryloyl groups has, for example, a dibasic acid anhydride or a carboxylic acid, a hydroxyl group and two or more (meth) acryloyl groups in the molecule. It can be obtained by reacting with a polyfunctional (meth) acrylate.

(C) Polybasic acid anhydride
In accordance with the present invention, the polybasic acid anhydride (C) used in the present invention increases the acid value of the photosensitive resin composition containing the photopolymerizable unsaturated resin, thereby increasing the pattern formability, development characteristics and development. Used to improve speed.

Examples of polybasic acid anhydrides (C) include succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic dianhydride 3,3′-4,4′-benzophenone tetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride), glycerol tris (trimellitic anhydride), phthalic anhydride, hexahydrophthalic anhydride, methylhydrophthalic acid Anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl -3-Cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydrophthalic anhydride-maleic acid Selected from the group consisting of anhydride adducts, dodecenyl succinic anhydride, and methyl micmic anhydride, preferably the group consisting of succinic anhydride, trimellitic anhydride, and hexahydrophthalic anhydride Although not limited to these, one or more may be mentioned.

(D) Monofunctional or polyfunctional epoxy compound The monofunctional epoxy compound used in the present invention further improves the development characteristics of the photosensitive resin composition by controlling the acid value of the photopolymerizable unsaturated resin. Used to improve. Preferably, according to the present invention, the solid content of the photosensitive resin composition has an acid value in the range of 20-120 mg KOH / g. Therefore, the amount of the monofunctional epoxy compound is preferably selected so as to satisfy the acid value.

  Specific examples of monofunctional epoxy compounds include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether. , Hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl Ether, propargyl glycidyl ether, 2-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyphenyl glycidyl ether, p-butylphenyl glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether , Benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1, 2-epoxy-4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexeneoxy And propylene oxide may be mentioned.

  The polyfunctional epoxy compound used in the present invention plays a role of controlling the development speed by increasing the molecular weight of the photopolymerizable unsaturated resin.

Examples of polyfunctional epoxy compounds include polyglycidyl ethers of polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl ethers of polybasic acids, cyclohexene oxides obtained by epoxidizing compounds containing cyclohexene or cyclopentene with an oxidizing agent. Or a cyclopentene oxide containing compound may be mentioned. More specifically, examples of the multifunctional epoxy compound may include the following: alkylidene bisphenol polyglycidyl ether type epoxy resin, for example, bisphenol A type epoxy resin, bisphenol B type epoxy resin, bisphenol C type epoxy Resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol S type epoxy resin, and bisphenol Z type epoxy resin; the alkylidene bisphenol polyglycidyl ether type epoxy resin with water Water-added bisphenol-type diglycidyl ether obtained by adding glycidyl ether; glycidyl ether of aliphatic polyhydric alcohol such as ethylene glycol diglycidyl ether 1,3-propylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol di Glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (glycidyloxy) Chill) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether And dipentaerythritol hexaglycidyl ether; a polyglycidyl ether of a polyether polyol obtained by adding two or more alkylene oxides to a polyhydric alcohol such as propylene glycol, trimethylolpropane and glycerin; a novolac-type epoxy compound; For example, phenol novolac type epoxy compound, biphenyl novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A novolac type epoxy compound Dicyclopentadiene novolac type epoxy compounds; cycloaliphatic epoxy compounds such as 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy -5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxy Cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, bis (3,4-epoxycyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane), Seo propylidene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylenebis (3,4-epoxycyclohexane carboxylate), and 1,2-epoxy-2-epoxy ethylcyclohexane; glycidyl diacid Esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, and diglycidyl dimer; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, and N, N-diglycidyl aniline; Cyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin, and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadiene Oxide; naphthalene epoxy compounds; triphenylmethane-type epoxy compound; and dicyclopentadiene epoxy compounds.

  Products commercially available as multifunctional epoxy compounds may include, for example, the following: BREN-S, EPPN-201, EPPN-501N, EOCN-1020, GAN, and GOT (Nippon Kayaku) Adeka Resin EP-4000, Adeka Resin EP-4003, Adeka Resin EP-4080, Adeka Resin EP-4085, Adeka Resin EP-4088, Adeka Resin EP-4100, Adeka Resin EP-4900, Adeka Resin ED-505, Adeka Resin ED-506, Adeka Resin KRM-2110, Adeka Resin KRM-2199, and Adeka Resin KRM-2720 (ADEKA Corporation); R-508, R-531, and R-710 (Mitsui Chemicals); Epicoat 190P, Epicoat 1 1P, Epicoat 604, Epicoat 801, Epicoat 825, Epicoat 871, Epicoat 872, Epicoat 1031, Epicoat RXE15, Epicoat YX-4000, Epicoat YDE-205, and Epicoat YDE-305 (Japan Epoxy Resin Co., Ltd.); Sumiepoxy ELM-120 And Sumiepoxy ELM-434 (Sumitomo Chemical Co., Ltd.); Denacol EM-150, Denacol EX-201, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-322, Denacol EX- 411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-614, Denacol EX-711, Denacol EX- 21, Denacol EX-731, Denacol EX-811, Denacol EX-821, Denacol EX-850, Denacol EX-851, and Denacol EX-911 (Nagase ChemteX Corporation); Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 80MF, Epolite 100MF, Epolite 1500NP, Epolite 1600, Epolite 3002, Epolite 4000, Epolite FR-1500, Epolite M-1230, and Epolite EHDG-L (Kyoeisha Chemical Co., Ltd.) SB-20 (Okamura Oil Co., Ltd.); Epicron 720 (Dainippon Ink &Chemicals); UVR-6100, UVR-6105, UVR -6110, UVR-6200, and UVR-6228 (Union Carbide Corporation); Ceroxide 2000, Ceroxide 2021, Ceroxide 2021P, Ceroxide 2081, Ceroxide 2083, Ceroxide 2085, Ceroxide 3000, Sicomer A200, Sicomer MlOO, Sicomer M10T 301, Epolide GT-302, Epolide 401, Epolide 403, Epolide HD300, EHPE-3150, ETHB, and Epoblend (Daicel Corporation); PY-306, 0163, and DY-022 (Ciba Specialty Chemicals Corporation); Santo Tote ST0000 Epototo YD-011, Epototo YD-115, Epototo YD-127, Epototo YD 134, Epototo YD-172, Epototo YD-6020, Epototo YD-716, Epototo YD-7011R, Epototo YD-901, Epototo YDPN-638, Epototo YH-300, Neototo PG-202, and Neototo PG-207 Co., Ltd.); and Bremmer G etc. (NOF Corporation).

2. Functional monomer having at least one ethylenically unsaturated bond The functional monomer having at least one ethylenically unsaturated bond is a reactive unsaturated compound and is a monomer commonly used in photosensitive resin compositions Alternatively, monofunctional or polyfunctional esters of acrylic acid or methacrylic acid that are oligomers and have at least one ethylenically unsaturated double bond could be used.

  The content of the functional monomer having at least one ethylenically unsaturated bond may be 1 to 50% by weight based on the total weight of the photosensitive resin composition excluding the remaining amount of solvent. If the content of the functional monomer having at least one ethylenically unsaturated bond is within the above range, the pattern is easily formed, and it is advantageous in the development margin aspect because the lower over-development does not occur during the development process. .

  The functional monomer having at least one ethylenically unsaturated bond is a reactive unsaturated compound, and examples of functional monomers having at least one ethylenically unsaturated bond include, but are not limited to, ethylene glycol dia Chlorates, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate Bisphenol A epoxy acrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol dimethacrylate, and 1,6-hexanediol dimethacrylate At least one member selected from the group consisting may be mentioned.

Examples of commercially available functional monomers having at least one ethylenically unsaturated bond may include the following products: As a commercial product of monofunctional (meth) acrylates, Allomix M-101 , Alomix M-111 and Alomix M-114 (Toagosei Co., Ltd.); Kayarad TC-110S and Kayarad TC-120S (Nippon Kayaku Co., Ltd.); and V-158 and V-2311 (Osaka Organic Chemical Co., Ltd.) Company).
Commercial products of bifunctional (meth) acrylate products include Alomix M-210, Alomix M-240, and Alomix M-6200 (Toagosei Co., Ltd.); Kayarad HDDA, Kayarad HX-220 and Kayarad R- 604 (Nippon Kayaku Co., Ltd.); and V260, V312 and V335 HP (Osaka Organic Chemical Industries, Ltd.).
Commercial products of tri- or higher functional (meth) acrylate products include Alomix M-309, Alomix M-400, Alomix M-405, Alomix M-450, Alomix M-7100, Alomix M-8030 and Alomix M-8060 (Toagosei Co., Ltd.); Kayarad TMPTA, Kayarad DPCA-20, Kayarad DPCA-30, Kayarad DPCA-60 and Kayarad DPCA-120 (Nippon Kayaku Co., Ltd.); and V-295 , V-300, V-360, V-GPT, V-3PA and V-400 (Osaka Organic Chemical Co., Ltd.). The above compounds may be used alone or in combination of two or more thereof.

  The content of the functional monomer having at least one ethylenically unsaturated bond is 1 to 50% by weight, preferably 1 to 20% by weight, based on the total photosensitive resin composition excluding the remaining solvent. And more preferably in the range of 1-15% by weight. When the content of the functional monomer having at least one ethylenically unsaturated bond is in the range of 1 to 50% by weight, the sensitivity is improved in the presence of oxygen, and the pattern is easily formed. Since the coating surface is not roughened after the formation of the coat and the excessive development of the lower portion does not occur during the development, the development margin aspect is advantageous.

3. Polymerization initiator
The polymerization initiator in the present invention is a functional monomer having at least one ethylenically unsaturated bond when exposed to synchrotron radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray, or A compound that produces an active species capable of initiating polymerization of a monofunctional or polyfunctional epoxy compound.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, o-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, dikenone compounds, α -Diketone compounds, polynuclear quinone compounds, thioxanthone compounds, diazo compounds, imide sulfonate compounds, oxime compounds, carbazole compounds, and sulfonium borate compounds. These compounds are components that generate an active radical, an active acid, or both an active radical and an active acid by exposure, and they can be used alone or in a mixture of two or more thereof.

  Examples of acetophenone compounds include 2,2′-diethoxyacetophenone, 2,2′-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyl. Dichloroacetophenone, 4-chloroacetophenone, 2,2′-dichloro-4-phenoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and 2-benzyl-2 Mention may be made of -dimethylamino-1- (4-morpholinophenyl) -butan-1-one.

  Examples of benzophenone compounds include benzophenone, benzoylbenzoate, methylbenzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis ( Mention may be made of diethylamino) benzophenone, 4,4′-dimethylaminobenzophenone, 4,4′-dichlorobenzophenone and 3,3′-dimethyl-2-methoxybenzophenone.

  Examples of the thioxanthone compound may include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone.

  Examples of benzoin-based compounds may include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

  Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (3′4′-dimethoxystyryl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4′-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy Ft-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-trichloromethyl (piperonyl) -6-triazine, and 2-4-trichloromethyl (4'-methoxystyryl)- There may be mentioned 6-triazine.

  Preferably, examples of polymerization initiators include p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyldimethyl ketal, benzophenone, benzoin propyl ether, diethylthioxanthone, 2, 4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 9-phenylacridine, 3-methyl-5-amino -((S-triazin-2-yl) amino) -3-phenylcoumarin, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 1-phenyl-1,2-propanedione-2- (o -Ethoxycarbonyl) oxime, o-benzoyl-4 '-(benzomercapto) ben Zoyl-hexyl-ketoxime, 2,4,6-trimethylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-tri-alkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, and Although 1 or more types selected from the group which consists of these mixtures may be mentioned, it is not limited to these.

  The content of the polymerization initiator may be 0.1 to 10% by weight based on the total weight of the photosensitive resin composition excluding the remaining amount of the solvent. When the content of the polymerization initiator is within the above range, the pattern of the colored layer is easily obtained, and curing by exposure is sufficiently performed, so that the formed colored layer is sufficiently applied to the substrate during development. Can be glued.

4). Black organic pigment
The black organic pigment means an organic pigment colored black, and represents a black color similar to carbon black which is an inorganic pigment.

  Examples of the black organic pigment include, but are not limited to, at least one selected from aniline black, lactam black, and perylene black.

  Furthermore, the photosensitive resin composition according to the present invention may additionally contain a black inorganic pigment together with a black organic pigment, wherein the black inorganic pigment is a group consisting of carbon black, chromium oxide, iron oxide and titanium black. And the content thereof is 0.1 to 70 parts by weight with respect to 100 parts by weight of the black organic pigment.

  If the content of organic pigment is increased, the melt flow phenomenon becomes worse and it becomes difficult to form a pattern on a thick film such as a column spacer. Therefore, it is important to control the mixing ratio of the organic pigment and the inorganic pigment.

  The content of both the black organic pigment or the black organic pigment and the black inorganic pigment may be 10 to 60% by weight based on the total weight of the photosensitive resin composition excluding the remaining solvent. When the content of the black inorganic pigment is within the above range, the optical density is prevented from being too low, the processability, for example, development characteristics are improved, and a high optical density is achieved. The

  On the other hand, a dispersant may be used to disperse the pigment in the photosensitive resin composition according to the present invention. This dispersant can be used by adding it to the pigment, for example, by treating the surface of the pigment with a dispersant in advance, or the dispersant is dispersed in preparing the photosensitive resin composition. It can be used by adding the agent directly with the pigment.

5. Solvent The solvent used in the present invention is compatible with the components of the photosensitive resin composition, but does not react with these components.

  Examples of solvents may include compounds including: alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; cellosolve acetate such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; carbitol such as methyl ethyl carbitol, diethyl Carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, die Lenglycol methyl ethyl ether and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetates; aromatic hydrocarbons such as toluene and xylene; ketones such as Methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylate alkyl esters, such as Ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate, and ethyl Lactate; alkyloxyacetate esters such as methyloxyacetate, ethyloxyacetate, and butyloxyacetate; alkylalkoxyacetate esters such as methylmethoxyacetate, ethylmethoxyacetate, butylmethoxyacetate, methyl Ethoxyacetate and ethylethoxyacetate; 3-oxypropionate alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; alkyl 3-alkoxypropionate esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; alkyl 2-oxypropionate S Tells such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate; alkyl 2-alkoxypropionate esters such as methyl 2-methoxypropionate, ethyl 2 -Methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; alkyl monooxymonocarboxylate esters such as 2-oxy-2-methylpropionate esters such as methyl 2- Oxy-2-methylpropionate, and ethyl 2-oxy-2-methylpropionate, and 2-alkoxy-2-methylpropionate alkyl, such as methyl 2-methoxy-2-methylpropionate, and Ethyl 2-ethoxy-2-methyl Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxylactate, and methyl 2-hydroxy-3-methylbutyrate; and ketonate esters such as Ethyl pyrbert. Examples of solvents additionally include high-boiling solvents such as N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone Dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate may be mentioned.

  In view of compatibility and reactivity between the solvent of the resin composition of the present invention and other components, examples of preferred solvents in the above examples may include the following: glycol esters, such as ethylene glycol Monomethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether; and propylene glycol alkyl ether acetates such as propylene glycol methyl Ether acetate, as well as propylene glycol propyl ether acetate.

  The solvent is used in the remaining amount, and is preferably contained in an amount of 50 to 90% by weight with respect to 100% by weight of the total content of the photosensitive resin composition containing the solvent. When the content of the solvent is 50 to 90% by weight, the resin composition has an appropriate viscosity and the processability is improved.

6). Other Additives 1) Silane Coupling Agent The photosensitive resin composition of the present invention comprises a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and a combination thereof in order to improve adhesion properties to a substrate. A silane coupling agent having one or more reactive substituents selected from the group may be further included.

  Specific examples of silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyl Examples include trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and these may be used alone or in combination of two or more thereof.

  When a silane coupling agent is added, the addition amount of the silane coupling agent is preferably 0.001 to 20 parts by weight with respect to 100 parts by weight of the photopolymerizable binder resin.

2) Surfactant If necessary, the photosensitive resin composition of the present invention may further contain a surfactant in order to improve the covering property and prevent the formation of defects.

  Examples of surfactants include fluorosurfactants marketed under the following names: BM-1000 and BM-1100 (BM Chemie); Megaface F142D, F172, F173 and F183 (Dainippon Ink Chemical Co., Ltd.) Industrial); Fluorad FC-135, FC-170C, FC-430 and FC-431 (Sumitomo 3M Limited); Surflon S-112, S-113, S-131, S-141 and S-145 (Asahi Glass Co., Ltd.) And SH-28PA, SH-190, SH-193, SZ-6032 and SF-8428 (Toray Dow Corning Silicone).

  When the surfactant is added, the addition amount of the surfactant is preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the photopolymerizable binder resin.

  Furthermore, the photosensitive resin composition of the present invention may contain other additives such as antioxidants and stabilizers in specific amounts that do not degrade the physical properties of the composition.

  According to another aspect of the present invention, the present invention provides a light shielding spacer formed from the photosensitive resin composition. This spacer is characterized in that it has a dielectric constant of 8 F / m or less and an optical density of 1.0 or more.

  According to yet another aspect of the present invention, the present invention provides a liquid crystal display device comprising this spacer.

  Hereinafter, the present invention will be described in more detail with reference to the following examples as preferred embodiments.

Synthesis Example 1 Epoxy resin synthesis (xanthene derivative [a-1])
125.4 g of spiro (fluorene-9,9′-xanthene) -3 ′, 6′-diol was mixed with 0.1386 g of t-butylammonium bromide in a 3,000 ml three-necked round bottom flask and this After pouring 78.6 g of epichlorohydrin into a three-necked round bottom flask, the mixture was reacted by heating the mixture to 90 ° C. Once the spiro (fluorene-9,9′-xanthene) -3 ′, 6′-diol has been completely removed by liquid chromatography analysis, the reactants are cooled to 30 ° C. and then cooled to the cooled reactants. Three equivalents of 50% aqueous NaOH were added slowly. Subsequently, when epichlorohydrin was completely removed by liquid chromatography analysis, the mixture was extracted with dichloromethane and washed three times with water. The resulting organic layer is dried over magnesium sulfate and subjected to vacuum distillation to remove dichloromethane and recrystallized using a mixture of dichloromethane and methanol (mixing ratio 50 volume%: 50 volume%). To produce an epoxy compound.

  After mixing 1 equivalent of the synthesized epoxy compound with 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalents of acrylic acid, the mixture is Further, it was mixed with 8.29 g of propylene glycol monomethyl ether acetate as a solvent to form a reaction solution. The reactants were dissolved by heating the reaction solution to a temperature range of 90-100 ° C. while blowing air into the reaction solution at a flow rate of 25 ml / min. When the reaction solution was in a white turbid state, the reaction solution was completely dissolved by heating the reaction solution to 120 ° C. The solution was agitated until the acid value of the solution was measured and the solution had an acid value of less than 1.0 mg KOH / g (at which time the solution was clear and had a high viscosity). It was. Eleven hours were required to reach the target acid number of 0.8. After completion of the reaction, the reactor temperature was lowered to room temperature, yielding a clear colorless solid.

Synthesis Example 2 Epoxy resin synthesis (xanthene derivative [a-2])
125.4 g of 9,9-diphenyl-9H-xanthene-3,6-diol was mixed with 0.1386 g of t-butylammonium bromide in a 3,000 ml three-necked round bottom flask and the three-necked round bottom flask After injecting 78.6 g of epichlorohydrin into the mixture, the mixture was reacted by heating the mixture to 90 ° C. When 9,9-diphenyl-9H-xanthene-3,6-diol was completely removed by liquid chromatography analysis, the reaction was cooled to 30 ° C. and then 3 equivalents of 50 % NaOH aqueous solution was added slowly. Subsequently, when epichlorohydrin was completely removed by liquid chromatography analysis, the mixture was extracted with dichloromethane and washed three times with water. The resulting organic layer is dried over magnesium sulfate and subjected to vacuum distillation to remove dichloromethane and recrystallized using a mixture of dichloromethane and methanol (mixing ratio 50 volume%: 50 volume%). To produce an epoxy compound.

  After mixing 1 equivalent of the synthesized epoxy compound with 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalents of acrylic acid, the mixture is Further, it was mixed with 8.29 g of propylene glycol monomethyl ether acetate as a solvent to form a reaction solution. The reactants were dissolved by heating the reaction solution to a temperature range of 90-100 ° C. while blowing air into the reaction solution at a flow rate of 25 ml / min. When the reaction solution was in a white turbid state, the reaction solution was completely dissolved by heating the reaction solution to 120 ° C. The solution was agitated until the acid value of the solution was measured and the solution had an acid value of less than 1.0 mg KOH / g (at which time the solution was clear and had a high viscosity). It was. Eleven hours were required to reach the target acid number of 0.8. After completion of the reaction, the reactor temperature was lowered to room temperature, yielding a clear colorless solid.

Synthesis Example 3 Epoxy resin synthesis (xanthene derivative [a-3])
145.2 g of 3,6-dimethoxyspiro (fluorene-9,9′-xanthene) -3 ′, 6′-diol in 0.1423 g of t-butylammonium bromide in a 3,000 ml three-necked round bottom flask After mixing and injecting 73.6 g of epichlorohydrin into the three-necked round bottom flask, the mixture was reacted by heating the mixture to 90 ° C. When 3,6-dimethoxyspiro (fluorene-9,9′-xanthene) -3 ′, 6′-diol was completely removed by liquid chromatography analysis, the reactants were cooled to 30 ° C. before the cooling. 3 equivalents of 50% aqueous NaOH was slowly added to the reaction mass. Subsequently, when epichlorohydrin was completely removed by liquid chromatography analysis, the mixture was extracted with dichloromethane and washed three times with water. The resulting organic layer is dried over magnesium sulfate and subjected to vacuum distillation to remove dichloromethane and recrystallized using a mixture of dichloromethane and methanol (mixing ratio 50 volume%: 50 volume%). Thus, an epoxy compound was formed.

  After mixing 1 equivalent of the synthesized epoxy compound with 0.004 equivalent of t-butylammonium bromide, 0.001 equivalent of 2,6-diisobutylphenol, and 2.2 equivalents of acrylic acid, the mixture is And mixed with 8.29 g of propylene glycol monomethyl ether acetate as a solvent to form a reaction solution. The reactants were dissolved by heating the reaction solution to a temperature range of 90-100 ° C. while blowing air into the reaction solution at a flow rate of 25 ml / min. When the reaction solution was in a white turbid state, the reaction solution was completely dissolved by heating the reaction solution to 120 ° C. The solution was agitated until the acid value of the solution was measured and the solution had an acid value of less than 1.0 mg KOH / g (at which time the solution was clear and had a high viscosity). It was. Eleven hours were required to reach the target acid number of 0.8. After completion of the reaction, the reactor temperature was lowered to room temperature, yielding a clear colorless solid.

Production Example 1 Production of photopolymerizable unsaturated resin 43 g of the polymerizable compound obtained in Synthesis Example 1 (hereinafter referred to as “compound a-1”), 33.6 g of acrylic acid (hereinafter referred to as “compound b-1”) , 0.04 g 2,6-di-tert-butyl-p-cresol, 0.21 g tetrabutylammonium acetate, and 18 g propylene glycol-1-monomethyl ether-2-acetate into the reaction flask These materials were agitated at 120 ° C. for 13 hours. The mixture was cooled to room temperature and 24 g of propylene glycol-1-monomethyl ether-2-acetate and 10 g of succinic anhydride (hereinafter referred to as “Compound c-1”) were added to the cooled mixture. Later, the mixture was stirred at 100 ° C. for 3 hours. To this mixture was further added 8 g of bisphenol Z glycidyl ether (hereinafter referred to as “Compound d-2”) and the material was added at 120 ° C. for 4 hours, 90 ° C. for 3 hours, and 60 ° C. for 2 hours. And after continuous stirring at 40 ° C. for 5 hours, the mixture is reprecipitated in water and alcohol to obtain a photopolymerizable unsaturated resin with alkaline development properties, which is a target material in powder form. Obtained. The resulting resin had a weight average molecular weight of 5,500 and an acid value of 105 mg KOH / g.

  This reaction product is obtained by adding compound b-1 (which is component (B)) with compound a-1 (which is component (A)) to form an epoxy adduct (AB). And the epoxy adduct (AB) is esterified with compound c-1 (this is component (C)) in an amount of 0.8 equivalents relative to 1 equivalent part of the hydroxyl groups of the epoxy adduct (AB). The resulting product is then combined with compound d-2 (which is an equivalent of 0.3 equivalent parts of epoxy groups of compound d-2 to 1 equivalent part of hydroxyl groups of the epoxy adduct (AB)). It was obtained by further esterification with component (D).

  Furthermore, this epoxy adduct (AB) has a structure in which the carboxyl group of compound b-1 is added at a ratio of 1.0 to the epoxy group of compound a-1.

Production Example 2 Production of photopolymerizable unsaturated resin 16.95 g of the polymerizable compound obtained in Synthesis Example 2 (hereinafter referred to as “compound a-2”), 4.43 g of acrylic acid (compound b-1), 6 g of After injecting 2,6-di-tert-butyl-p-cresol, 0.11 g tetrabutylammonium acetate, and 14.25 g propylene glycol-1-monomethyl ether-2-acetate into the reaction flask, these The material was agitated at 120 ° C. for 16 hours. The mixture was cooled to room temperature and 9.31 g of propylene glycol-1-monomethyl ether-2-acetate, 7.41 g of hexahydrophthalic anhydride (hereinafter “Compound c-2”) was cooled to room temperature. ) And 0.25 g of tetra-n-butylammonium acetate, the mixture is stirred for 4 hours at 70 ° C. and reprecipitated in water and alcohol to form a powder form. As a target material, a photopolymerizable unsaturated resin having alkali development characteristics was obtained. The resulting resin had a weight average molecular weight of 4,500 and an acid value of 110 mg KOH / g.

  This reaction product is obtained by adding compound b-1 (which is component (B)) with compound a-2 (which is component (A)) to form an epoxy adduct (AB). And the epoxy adduct (AB) is esterified with compound c-2 (this is component (C)) in an amount of 0.8 equivalents relative to 1 equivalent part of the hydroxyl groups of the epoxy adduct (AB). Was obtained.

  Furthermore, this epoxy adduct (AB) has a structure in which the carboxyl group of compound b-1 is added at a ratio of 1.0 to the epoxy group of compound a-2.

Production Example 3 Production of photopolymerizable unsaturated resin 16.95 g of the polymerizable compound obtained in Synthesis Example 3 (hereinafter referred to as “compound a-3”), 4.43 g of acrylic acid (compound b-1), 6 g of After injecting 2,6-di-tert-butyl-p-cresol, 0.11 g tetrabutylammonium acetate, and 14.25 g propylene glycol-1-monomethyl ether-2-acetate into the reaction flask, these The material was agitated at 120 ° C. for 16 hours. The mixture was cooled to room temperature, and 9.31 g propylene glycol-1-monomethyl ether-2-acetate, 7.41 g hexahydrophthalic anhydride (compound c-2) and 0. After adding 25 g of tetra-n-butylammonium acetate, the mixture is stirred at 70 ° C. for 4 hours and reprecipitated in water and alcohol to form the target material in powder form, alkali A photopolymerizable unsaturated resin having development characteristics was obtained. The resulting resin had a weight average molecular weight of 3,500 and an acid value of 105 mg KOH / g.

  This reaction product is obtained by adding compound b-1 (which is component (B)) with compound a-3 (which is component (A)) to form an epoxy adduct (AB). And the epoxy adduct (AB) is esterified with compound c-2 (this is component (C)) in an amount of 0.8 equivalents relative to 1 equivalent part of the hydroxyl groups of the epoxy adduct (AB). Was obtained.

  Furthermore, this epoxy adduct (AB) has a structure in which the carboxyl group of compound b-1 is added at a ratio of 1.0 to the epoxy group of compound a-2.

Production Example 4 Production of Black Organic Pigment Composition An organic black material (Black 582 as lactam black produced by Ciba Geigy Corporation), a dispersant and a polymer for the dispersion, based on solids content, 50 parts by weight, 8 After mixing at parts by weight and 8 parts by weight, propylene glycol monomethyl ether acetate (PGMEA) as a solvent was added to the mixture and the resulting mixture had a solids concentration of 25% by weight. The total weight of this dispersion was 50 g, which was stirred with a stirrer to premix these materials. This mixture was subjected to dispersion treatment with a paint shaker at a temperature of 25-60 ° C. for 6 hours. Zirconia beads with a diameter of 0.3 mm were used as beads and added to this mixture at the same weight as the dispersion. A black pigment composition was prepared by separating the beads from the dispersion by a filter after the dispersion was completed.

Production Example 5 Production of composition of black organic pigment and inorganic pigment In place of 50 parts by weight of lactam black in Production Example 4, 35 parts by weight of lactam black and 15 parts by weight of carbon black (manufactured by Degussa) were used. A pigment composition was prepared using the same method as in Production Example 4.

Production Example 6 Production of composition of black organic pigment and inorganic pigment In place of 50 parts by weight of lactam black in Production Example 4, 30 parts by weight of lactam black and 20 parts by weight of carbon black (produced by Degussa) were used. A pigment composition was prepared using the same method as in Production Example 4.

Production Example 7 Production of composition of black organic pigment and inorganic pigment In place of 50 parts by weight of lactam black in Production Example 4, 25 parts by weight of lactam black and 25 parts by weight of carbon black (produced by Degussa) were used. A pigment composition was prepared using the same method as in Production Example 4.

Production Example 8 Production of composition of black organic pigment and inorganic pigment, except that 15 parts by weight of lactam black and 35 parts by weight of carbon black (produced by Degussa) were used instead of 50 parts by weight of lactam black in Production Example 4. A pigment composition was prepared using the same method as in Production Example 4.

Production Example 9 Production of black inorganic pigment composition The same method as in Production Example 4 except that 50 parts by weight of carbon black (produced by Degussa) was used instead of 50 parts by weight of lactam black in Production Example 4. Used to prepare a pigment composition.

Example 1
1.0874 g of photopolymerizable unsaturated resin obtained in Production Example 1, 0.7249 g of dipentaerythritol hexaacrylate, 0.0651 g of oxime photoinitiator (OXE-02, Ciba-Geigy Corporation), 0.0042 g Leveling surfactant (silicone surfactant BYK 333, BYK Corporation), 0.0084 g of adhesion assistant (KBE-9007, Shin-Etsu Chemical Co., Ltd.), and 8.9 g of black obtained in Production Example 4 The organic pigment composition (lactam black: carbon black = 50 parts by weight: 0 part by weight) has a black alkali developing property by stirring well in 9.2094 g of propylene glycol-1-monomethyl ether-2-acetate. A photosensitive resin composition was obtained.

Example 2
1.0874 g of photopolymerizable unsaturated resin obtained in Production Example 2, 0.7249 g of dipentaerythritol hexaacrylate, 0.0651 g of oxime photoinitiator (OXE-02, Ciba-Geigy Corporation), 0.0042 g Leveling surfactant (silicone surfactant BYK 333, BYK Corporation), 0.0084 g of adhesion assistant (KBE-9007, Shin-Etsu Chemical Co., Ltd.), and 8.9 g of black obtained in Production Example 4 The organic pigment composition (lactam black: carbon black = 50 parts by weight: 0 part by weight) has a black alkali developing property by stirring well in 9.2094 g of propylene glycol-1-monomethyl ether-2-acetate. A photosensitive resin composition was obtained.

Example 3
1.0723 g photopolymerizable unsaturated resin obtained in Production Example 3, 0.7184 g dipentaerythritol hexaacrylate, 0.0651 g oxime photoinitiator (OXE-02, Ciba-Geigy Corporation), 0.0042 g Leveling surfactant (silicone surfactant BYK 333, BYK Corporation), 0.0084 g of adhesion assistant (KBE-9007, Shin-Etsu Chemical Co., Ltd.), and 8.9 g of black obtained in Production Example 4 An organic pigment composition (lactam black: carbon black = 50 parts by weight: 0 parts by weight) was mixed well in 9.2094 g of propylene glycol-1-monomethyl ether-2-acetate to obtain a black alkali development type photosensitivity. A resin composition was obtained.

Example 4
In Example 1, instead of the black organic pigment composition of Production Example 4, the composition of the black organic pigment and inorganic pigment of Production Example 5 (lactam black: carbon black = 35 parts by weight: 15 parts by weight) is used. Except for this, an alkali development type photosensitive resin composition was produced in the same manner as used in Example 1.

Example 5
In Example 1, instead of the black organic pigment composition of Production Example 4, the composition of the black organic pigment and inorganic pigment of Production Example 6 (lactam black: carbon black = 30 parts by weight: 20 parts by weight) is used. Except that, an alkali developing type photosensitive resin composition was produced in the same manner as in Example 1.

Comparative Example 1
1.7538 g of bisphenol type binder (ZFR-2041H, Nippon Kayaku Co., Ltd.), 0.7249 g of dipentaerythritol hexaacrylate, 0.0651 g of oxime photoinitiator (OXE-02, Ciba-Geigy Corporation), 0042 g of leveling surfactant (silicone surfactant BYK 333, manufactured by BYK Corporation), 0.0084 g of adhesion assistant (KBE-9007, Shin-Etsu Chemical Co., Ltd.), and 8.9 g of Production Example 6 The resulting black organic pigment and inorganic pigment composition was mixed well in 8.543 g of propylene glycol-1-monomethyl ether-2-acetate to obtain a photosensitive resin composition having black alkaline development characteristics. It was.

Comparative Example 2
2.398 g of cardo binder (CBR-D07-3, Kyungin Synthetic Corporation), 0.7249 g of dipentaerythritol hexaacrylate, 0.0651 g of oxime photoinitiator (OXE-02, Ciba-Geigy Corporation); 0042 g of leveling surfactant (silicone surfactant BYK 333, BYK Corporation), 0.0084 g of adhesion aid (KBE-9007, Shin-Etsu Chemical Co., Ltd.), and 8.9 g of Production Example 6 were obtained. The composition of the black organic pigment and the inorganic pigment was thoroughly stirred in 7.6188 g of propylene glycol-1-monomethyl ether-2-acetate to obtain a photosensitive resin composition having black alkaline development characteristics. .

Comparative Example 3
In Example 1, instead of the black organic pigment composition of Production Example 4, the composition of the black organic pigment and inorganic pigment of Production Example 7 (lactam black: carbon black = 25 parts by weight: 25 parts by weight) is used. Except that, an alkali developing type photosensitive resin composition was produced using the same method as in Example 1.

Comparative Example 4
In Example 1, instead of the black organic pigment composition of Production Example 4, the composition of the black organic pigment and inorganic pigment of Production Example 8 (lactam black: carbon black = 15 parts by weight: 35 parts by weight) is used. Except that, an alkali developing type photosensitive resin composition was produced using the same method as in Example 1.

Comparative Example 5
In Example 1, instead of the black organic pigment composition of Production Example 4, the black inorganic pigment composition of Production Example 9 (lactam black: carbon black = 0 parts by weight: 50 parts by weight) was used. Using the same method as in Example 1, an alkali development type photosensitive resin composition was produced.

Formation of Image Pattern The photosensitive resin composition of the present invention is applied to a desired thickness on a pretreated substrate by conventional coating methods such as spin or slit coating methods, roll coating methods, screen printing methods and applicator methods. For example, a film was formed by coating with a thickness of 2-25 μm and heating the coating at a temperature of 70-90 ° C. for 1-10 minutes to remove the solvent.

In order to form a necessary pattern on the obtained film, active rays of 200 to 500 nm were irradiated through a mask having a predetermined shape. Examples of light sources used for irradiation can include low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, and argon gas lasers, and if necessary further X-rays and electron beams. Can be mentioned. The amount of exposure varies depending on the type and amount of each component and the dry film thickness, but does not exceed 500 mJ / cm ² when using a high-pressure mercury lamp (measured by a 365 nm sensor).

  After performing the exposure process, an alkaline aqueous solution as a developer is used to dissolve and remove unnecessary portions, thereby allowing only the portions exposed to light to remain. To do. The image pattern obtained by development was cooled to room temperature and post-baked at 230 ° C. for 20 minutes in a hot air circulating drying oven to produce an image pattern.

Resolution The resolution of the obtained image pattern was measured by observing the minimum size of the formed colored spacer using a micro optical microscope.

Measurement of optical density Absorbance is the amount of light when the light intensity becomes constant after light of a given wavelength has passed through a specific layer, and optical density is calculated by dividing this absorbance value by thickness. can get. When light having a light intensity of I _{0 in} a specific wavelength band passes through a specific layer and the light intensity becomes I, the optical density is defined as log ₁₀ (I ₀ / I). . The luminous intensity of light in a specific wavelength band was measured using an optical density meter (361T table top transmittance densitometer manufactured by X-Light Corporation).

Measurement of Elastic Recovery Rate After coating the black photosensitive resin composition produced in Examples and Comparative Examples on a glass substrate using a spin coater, the applied composition was dried at 90 ° C. for 2.5 minutes. To form a film. A pattern mask was placed on the resulting film, and 100 mJ / cm ² light having a wavelength of 365 nm was irradiated onto the film. Thereafter, this film was developed at 23 ° C. for 1 minute using a 1% by weight diluted aqueous solution of potassium hydroxide, and then the developed film was washed with pure water for 1 minute. Unnecessary portions were removed, leaving only the spacer pattern. The formed spacer pattern was cured by heating in an oven at 230 ° C. for 30 minutes to give a colored spacer pattern.

  Coloring having a thickness (T) of 3.7 (± 0.2) μm and a width (W) of 35 (± 2) μm using the black photosensitive resin compositions produced in Examples and Comparative Examples A spacer was manufactured. The compression displacement and elastic recovery rate of the colored spacer were measured according to the following method using an elastic modulus measuring device (DUH-W201S) manufactured by Shimadzu Corporation of Japan.

A flat surface perpetrator with a diameter of 50 μm was used as the penetrator to compress the pattern and the measurement principle used a load-unload method. The loads applied in this test were 300 mN and 400 mN. The loading rate and holding time were kept constant at 0.45 gf / sec and 3 sec, respectively. The elastic recovery rate was obtained by measuring the thickness of the pattern with and without a load for 3 seconds using a flat surface perpetrator using a three-dimensional thickness measuring apparatus. Elastic recovery rate means the ratio of the recovered distance (D ₁ -D ₂ ) after a recovery time of 10 minutes to the distance (D ₁ ) of the pattern that is dented when the pattern is loaded, It is represented by the following formula 1:
[Formula 1]
Elastic recovery rate (%) = [(D ₁ −D ₂ ) × 100] / D ₁
Where D ₁ (μm) is the compressed displacement and D ₂ (μm) the distance of the pattern that is dented after the recovery time.

Measurement of Dielectric Constant A photoresist (PR) formed from the black photosensitive resin composition produced in Examples and Comparative Examples was coated on indium tin oxide (ITO) glass, and the applied photoresist ( PR) was dried on a hot plate at a temperature of 90 ° C. for 2.5 minutes to produce a film with a final thickness ranging from 1.5 to 2.5 μm. A gold (Au) electrode having a diameter of 300 μm was placed on this membrane to produce a sample. The capacitance value was measured using a HP 4294A precision impedance analyzer and the dielectric constant was obtained using this measured capacitance value and Equation 2 below.

[Formula 2]
C = ε ₀ × ε × A / d
Where C is the capacitance, ε ₀ is the dielectric constant under vacuum conditions, ε is the relative dielectric constant of the film, A is the electrode area, and d is the photoresist (PR) thickness. Indicates.

Evaluation criteria ○: Dielectric constant of 8 or less ×: Dielectric constant exceeding 8

Evaluation results The results of the tests are summarized in Table 1 below.

  As can be seen from Table 1, the optical density, dielectric constant, elastic recovery rate, and resolution of the present photosensitive resin compositions of Examples 1 to 6 are uniformly excellent.

  In particular, when Examples 1-5 are compared with Comparative Examples 1-5, Examples 1-5 are superior to Comparative Examples 1 and 2 in terms of resolution and are more dielectric than Comparative Examples 3, 4 and 5. It was excellent in terms of the rate, and it was recognized that it was superior in terms of the elastic recovery rate of 300 mN and 400 mN over Comparative Examples 1-5.

  Although the invention has been shown and described with reference to exemplary embodiments, it will be apparent to those skilled in the art that modifications and changes can be made without departing from the spirit and scope of the invention as defined by the claims. it is obvious. Therefore, the said embodiment is an illustration and should not be interpreted limitedly.

Claims (6)

Photopolymerizable unsaturated resin represented by Formula II

(In the formula, carbon labeled with ^*

Replaced with carbon labeled with ^* in one selected from the group consisting of ^:
L ¹ is C _1-10 alkylene, C _3-20 cycloalkylene or C _1-10 alkyleneoxy,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, C ₂ Selected from the group consisting of _-10 alkenyl and C _6-14 aryl;
R ⁸ is selected from the group consisting of C _1-10 alkyl, C _2-10 alkenyl and C _6-14 aryl, substituted or unsubstituted with hydrogen, halogen or hydroxy ,
n is an integer Ri der of 0,
R ¹⁰ —C (═O) —O— represents a residue of an unsaturated basic acid (B) or a residue of a polybasic acid anhydride (C), provided that R ¹⁰ —C (= At least one of O) —O— is a residue of an unsaturated basic acid (B), and at least one of R ¹⁰ —C (═O) —O— in the molecule is a polybasic acid anhydride ( A residue of C), and
R ¹² represents hydrogen or —C (═O) —R ¹⁰ . ). Photopolymerizable unsaturated resin represented by Formula III

(In the formula, carbon labeled with ^*

Replaced with carbon labeled with ^* in one selected from the group consisting of ^:
L ¹ is C _1-10 alkylene, C _3-20 cycloalkylene or C _1-10 alkyleneoxy,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, C ₂ Selected from the group consisting of _-10 alkenyl and C _6-14 aryl;
R ⁸ is selected from the group consisting of C _1-10 alkyl, C _2-10 alkenyl and C _6-14 aryl, substituted or unsubstituted with hydrogen, halogen or hydroxy ,
n is an integer Ri der of 0,
R ¹⁰ —C (═O) —O— represents a residue of an unsaturated basic acid (B) or —O—C (═O) —R ¹¹ —C (═O) —O—R ¹³ , , at least ^{1 R 10 -C (= O)} -O- in in the molecule is the residue of an unsaturated dibasic acid (B), and ^R 10 -C in the molecule (= O) -O- At least one of —O—C (═O) —R ¹¹ —C (═O) —O—R ¹³ ,
—O—C (═O) —R ¹¹ —C (═O) —O— represents the residue of the polybasic acid anhydride (C);
R ¹³ represents a hydrogen atom or —CH ₂ —CH (OH) —R ¹⁴ ,
—CH ₂ —CH (OH) —R ¹⁴ represents a residue of a monofunctional or multifunctional epoxy compound (D), where —CH ₂ —CH (OH) —R ¹⁴ is the multifunctional epoxy compound. Wherein the epoxy group of such a multifunctional epoxy compound may be bound to a hydroxyl group or a carboxyl group in the molecule represented by Formula III, and
R ¹² represents hydrogen, —C (═O) —R ¹⁰ or —CH ₂ —CH (OH) —R ¹⁴ . ). The unsaturated basic acid (B) is acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate-maleate, hydroxyethyl acrylate-maleate, hydroxypropyl methacrylate-maleate, hydroxypropyl acrylate- Maleate and at least one selected from the group consisting of dicyclopentadiene-maleate, and the polybasic acid anhydride (C) is succinic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride 2,2'-3,3'-benzophenone tetracarboxylic dianhydride, 3,3'-4,4'-benzophenone tetracarboxylic dianhydride, ethylene glycol bis (anhydrous trimellitate), glycerol tris (anhydrous) Trimellitate), phthalic anhydride , Hexahydrophthalic anhydride, methylhydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2 , 5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, adducts of trialkyltetrahydrophthalic anhydride and maleic anhydride, dodecenyl succinic anhydride, and methylhimine At least one selected from the group consisting of acid anhydrides,
The photopolymerizable unsaturated resin according to claim 1. The monofunctional epoxy compound (D) is glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether. Ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl Glycidyl ether, allyl glycidyl ether Propargyl glycidyl ether, 2-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxyphenyl glycidyl ether, p-butylphenyl glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, Benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy- 4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, and propylene oxide Comprising at least one selected from the group, and the polyfunctional epoxy compound (D) polyglycidyl ethers of polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl ethers of polybasic acid, a compound containing a cyclohexene oxide And at least one selected from the group consisting of compounds containing cyclopentene oxide,
The photopolymerizable unsaturated resin according to claim 2. A photosensitive resin composition comprising the photopolymerizable unsaturated resin according to claim 1, a functional monomer having at least one ethylenically unsaturated bond, a polymerization initiator, a black organic pigment, and a solvent,
Ri least Tanedea said black organic pigment is selected from the group consisting of aniline black, lactam black and perylene black,
The photosensitive resin composition comprises at least one black inorganic pigment selected from the group consisting of carbon black, chromium oxide, iron oxide and titanium black based on 100 parts by weight of the black organic pigment. In addition to weight parts,
Photosensitive resin composition. A photosensitive resin composition comprising the photopolymerizable unsaturated resin according to claim 2, a functional monomer having at least one ethylenically unsaturated bond, a polymerization initiator, a black organic pigment, and a solvent,
Ri least Tanedea said black organic pigment is selected from the group consisting of aniline black, lactam black and perylene black,
The photosensitive resin composition comprises at least one black inorganic pigment selected from the group consisting of carbon black, chromium oxide, iron oxide and titanium black based on 100 parts by weight of the black organic pigment. In addition to weight parts,
Photosensitive resin composition.