KR20090063976A - Composition for resin black matrix - Google Patents

Abstract

A photosensitive resin composition for resin black matrix and the resin black matrix using the same are provided to show excellent sensitivity, adhesion force to a substrate, heat resistance and pattern stability and to improve development margin and coating uniformity. A photosensitive resin composition for resin black matrix contains compounds with acrylate multi-functional groups in main chains represented by the formula 1. In the formula 1, R1 and R2 are identically or differently hydrogen or methyl group; Y is residue of acid anhydride; Z is residue of acid dianhydride; and a molar ratio of m and n is 100:0~0:100. The photosensitive resin composition comprises: 100 parts of compounds having the acrylate multi-functional groups; 0.1-99wt% of multi-functional monomers; 0.1-80 parts of silicone-based compound containing epoxy groups; 0.01-20 parts of photopolymerization initiator or photosensitizer; a pigment; and a solvent.

Description

Photosensitive resin composition for resin black matrix {Composition for Resin Black Matrix}

The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition for forming a black matrix of a liquid crystal display.

In the liquid crystal display (LCD) device, since the liquid crystal itself cannot emit light, a separate light source is installed at the rear of the device, and the contrast is adjusted by adjusting the intensity of the passing light through the liquid crystal installed in each pixel. . In more detail, the liquid crystal display device is a device for controlling the light transmittance by using the electrical properties of the liquid crystal material, the uniformity and the directionality is controlled by passing through various functional prism films or sheets by emitting light from the light source lamp on the back of the device It is a display device of an indirect light emission type that implements an image by passing light through a color filter to implement colors and controlling the contrast of each pixel by an electric method.

The color filter typically forms a black matrix on the upper surface of a plastic or glass substrate, and other colors such as red (R), green (G), and blue (B) are sequentially, stripe-like or mosaic-like. It is formed into a pattern.

Representative methods of manufacturing such color filters include dyeing, printing, pigment dispersion, electrodeposition, and the like. In particular, a photopolymerizable composition containing a color material is coated on a transparent substrate, and a pattern to be formed is exposed, and then a non-exposed part is exposed. The pigment dispersion method, which repeats a series of steps of removing and thermally curing the solvent with a solvent, is widely employed because of high accuracy of the position of the color filter pixel, film thickness, etc., excellent durability of light resistance, heat resistance, and less defects such as pinholes. have.

Here, the black matrix is necessary to prevent color mixing between the pixels of three colors of red (R), green (G), and blue (B) for high-definition and high contrast display of the liquid crystal display. In the case of an active matrix driving type TFT-LCD using a transistor, high light shielding property is required.

Conventionally, as a method of manufacturing a black matrix, a metal film such as chromium is formed on a substrate by vacuum deposition or the like, coated with a photosensitive resin, patterned by photolithography, and etched chromium. . The black matrix using chromium can be manufactured as a thin film, and has the advantage of obtaining chemical resistance and high light shielding performance, but due to the high light reflectivity, not only the display quality is deteriorated, but also a separate treatment process is required for total reflection. Since a vacuum deposition process such as chromium sputtering is involved, manufacturing costs increase, and there is a problem in that waste liquid generated after the etching process generates environmental pollution, which requires chromium etching.

Recently, studies on black matrices using resins have been actively conducted. The resins used in the black matrix produced by the pigment dispersion method are largely binder resins, which serve as a support, and polymer compounds that react with light during exposure to form a photoresist image, and light that reacts with light during exposure to form a photoresist image. It consists of the component of a synthetic monomer. In addition, it is produced by a photosensitive resin composition containing a pigment, a polymerization initiator, an epoxy resin, a solvent and other additives.

As binder resin used for a pigment dispersion method, For example, the polyimide resin of Unexamined-Japanese-Patent No. 60-237403; Photosensitive resin which consists of an acryl-type polymer and an azide compound as described in Unexamined-Japanese-Patent No. 1-200353, Unexamined-Japanese-Patent No. 4-7373, etc .; Japanese Patent Laid-Open No. 7-64281, Japanese Patent Laid-Open No. 7-64282, Japanese Patent Laid-Open No. 8-278630, Japanese Patent Laid-Open No. 6-1938 and Japanese Patent Laid-Open No. 5-339356; Photosensitive resin comprising an acrylic polymer described in Korean Patent Publication No. 97-6519, Korean Patent Registration No. 147191; Radical polymerization type photosensitive resin which consists of an acrylate monomer, an organic polymer binder, and a photoinitiator of Unexamined-Japanese-Patent No. 1-152449; A variety of proposals have been made, such as phenol resins described in Japanese Patent Laid-Open No. 4-163552 and Korean Patent Publication No. 92-5780, photosensitive resins composed of a crosslinking agent having a N-methylol structure and a photoacid generator.

Cardo-based resins are highly sensitive and excellent in heat resistance, shrinkage and transparency without being affected by oxygen, but have the disadvantage of poor adhesion and low flatness due to the bulky molecular structure. Since the content of the pigment is much higher than that of other colored photosensitive resin compositions, there is a problem in that adhesiveness and surface stability are lowered.

In addition, when the black matrix is manufactured, the amount of the coloring pigment should be extremely high in order to improve the light shielding properties. As a result, the viscosity increases during the preparation, making handling difficult, or the strength of the formed film or the adhesion to the substrate remarkably decreased. there is a problem. Therefore, since the film thickness becomes thick, when a high concentration of black matrix is formed, the light absorbing property of dispersed light blocking materials such as carbon black is high so that the light exposed to the bottom of the film does not reach, and there is a lack of photocuring under the film. Due to the excessive phenomenon of the pattern side surface during the process, there is a problem that the finally obtained pattern shape becomes a trapezoid.

In order to solve such a problem, an invention using a conventional acrylic resin binder having an alicyclic structure in the side chain and an acrylic binder resin having an aromatic structure in the side chain is disclosed in Korean Patent Registration No. 367472. In addition, the invention that can improve the adhesion to the substrate by using a triazine-based compound having an alkylthio group introduced into the photosensitive resin composition including an alkali-soluble resin binder and a polyfunctional monomer having an ethylenically unsaturated double bond as a photoinitiator It is disclosed in the registered patent 431461.

The present invention is to provide a photosensitive resin composition having excellent adhesion to the substrate, heat resistance, pattern stability as well as improved sensitivity and development margin to improve coating uniformity.

One embodiment of the present invention provides a photosensitive resin composition comprising a resin compound having a polyfunctional group structure having an acrylate group in the main chain, represented by the following formula (1).

In the above formula, R1 and R2 are the same as or different from each other, and are a hydrogen atom or a methyl group, Y is a residue of an acid anhydride, Z is a residue of an acid anhydride, and m: n is a molar ratio of 100: 0 to 0: 100. Ratio.

In the embodiment of the present invention (A) 100 parts by weight of a compound having an acrylate polyfunctional group in the main chain, represented by the formula (1); (B) 0.1 to 99 parts by weight of a multifunctional monomer; (C) 0.1 to 80 parts by weight of a silicone compound containing an epoxy group; (D) 0.01 to 20 parts by weight of the photopolymerization initiator or the photosensitizer; (E) pigment component; And (F) It provides a photosensitive resin composition containing a solvent.

In the photosensitive resin composition according to the embodiments of the present invention, the compound represented by Formula 1 is Y is maleic anhydride, Maleic anhydride, Succinic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride (cis-1,2,3,6-Tetrahydrophthalic Anhydride), 3,4,5,6-tetrahydrophthalic anhydride, Phthalic Anhydride, Itaconic Anhydride (Itaconic anhydride), 1,2,4-benzenetricarboxylic anhydride (1,2,4-Benzenetricarboxylic Anhydride), methyl-tetrahydrophthalic anhydride, citraconic anhydride, 2, 3-dimethylmaleic anhydride, 1-cyclopentene-1,2, -dicarboxylic anhydride, 1-Cyclopentene-1,2-Dicarboxylic anhydride, cis (5-norbornene-endo-2) , 3-dicarboxylic anhydride (cis-5-Norbonene-endo-2,3-Dicarboxylic Anhydride) and 1,8-naphtanic anhydride (1,8-Naphth alic Anhydride), and Z is 1,2,4,5-benzenetetracarboxylic dianhydride (1,2,4,5-Bezenetetracarboxylic Dianhydride), 4,4'-biphthalic dianhydride Water (4,4'-Biphthalic Dianhydride), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-Benzophenonetetracarboxylic Dianhydride), pyromellitic dianhydride (Pyromelitic Dianhydride) ), 1,4,5,8-naphthalenetetracarboxylic dianhydride (1,4,5,8-Naphthalenetetracarboxylic Dianhydride), 1,2,4,5-tetracarboxylic anhydride (1,2,4,5-Tetracarboxylic Anhydide ), Methylnorbornene-2,3-dicarboxylic anhydride, 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene ] Diphthalic Anhydride (4,4 '-[2,2,2-Trifluoro-1-Ethylidene] Diphthalic Anhydride), 4,4'-Oxydiphthalic Anhydride and Ethylene Glycol Bis (Anhydro Trimellitate) (Ethylene Glycol Bis ( Anhydro Trimelitate)) may be a residue of an acid dianhydride selected from.

In addition, the compound represented by the formula (1) has a ratio of m: n, which is a molar ratio of acid anhydride and acid anhydride, in the range of 100/0 to 50/50, in the range of 100/0 to 70/30, or 0/100 to 50 It may be in the range of / 50, the compound represented by Formula 1 may be included in 5 to 80% by weight of the total resin composition.

In addition, the pigment component (E) is carbon black having a particle size of 50 ~ 150nm, may be included in 1 to 90% by weight of the total resin composition.

In addition, one embodiment of the present invention provides a resin black matrix having a viscosity of 1 to 5 cps obtained by dispersion preparation of such a composition, which is coated per unit thickness (μm per unit in the pattern formed by lithography after coating it). ) The optical density may be 3.0 to 6.0.

According to the present invention, it is possible to provide a photosensitive resin composition having not only excellent sensitivity, adhesion to a substrate, heat resistance and pattern stability, but also a very stable developing pattern after post-baking at a low exposure amount of 30 mJ / cm 2, thereby providing an LCD device. It can be quickly responded to according to various kinds and sizes of can be usefully used in the liquid crystal display industry.

The present invention will be described in more detail as follows.

(1) a compound represented by formula (1)

The photosensitive resin composition according to the present invention includes a compound represented by Formula 1, which may be specifically obtained by the following method: a bisphenol fluorene type epoxy compound of Formula 2 and a (meth) acrylic acid of Formula 3 Reacted to synthesize a compound represented by the formula (4), and treated with an acid anhydride or acid 2 anhydride to give developability to the sock end, and then react the epoxy acrylate represented by the formula (5) to give a polyfunctional group To synthesize a compound of Formula 1.

Formula 1

Wherein R1 and R2 are the same as or different from each other, and are a hydrogen atom or a methyl group, Y is a residue of an acid anhydride, Z represents a residue of an acid anhydride, and m: n is a molar ratio of 100: 0 to 0: 100. Ratio.

 In the above formula, R1 is a hydrogen atom or a methyl group.

In the above formula, R1 is a hydrogen atom or a methyl group.

Wherein R2 is a hydrogen atom or a methyl group.

In the compound represented by Formula 1, the ratio of m: n, which is a molar ratio of acid anhydride and acid dianhydride, may be in a range of 100/0 to 0/100. Preferably, the ratio of m: n is in the range of 100/0 to 50/50, or 0/100 to 50/50.

In the compound represented by the formula (1), Y is maleic anhydride, Succinic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride (cis-1,2,3,6- Tetrahydrophthalic Anhydride, 3,4,5,6-Tetrahydrophthalic Anhydride (3,4,5,6-Tetrahydrophthalic Anhydride), Phthalic Anhydride, Itaconic Anhydride, 1,2,4- Benzene Tricarboxylic Anhydride (1,2,4-Benzenetricarboxylic Anhydride), Methyl-Tetrahydrophthalic Anhydride, Citraconic Anhydride, 2,3-Dimethylmaleic Anhydride (2,3-Dimethylmaleic Anhydride) Anhydride), 1-cyclopentene-1,2, -dicarboxylic anhydride (1-Cyclopentene-1,2-Dicarboxylic anhydride), cis (5-norbornene-endo-2,3-dicarboxylic acid anhydride (cis-5- Residues of acid anhydrides selected from Norbonene-endo-2,3-Dicarboxylic Anhydride) and 1,8-Naphthalic Anhydride There.

And Z is 1,2,4,5-benzenetetracarboxylic dianhydride (1,2,4,5-Bezenetetracarboxylic Dianhydride), 4,4'-biphthalic dianhydride (4,4'-Biphthalic Dianhydride), 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-Benzophenonetetracarboxylic Dianhydride), pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydrides (1,4,5,8-Naphthalenetetracarboxylic Dianhydride), 1,2,4,5-tetracarboxylic anhydride (1,2,4,5-Tetracarboxylic Anhydide), methylnorbornene-2,3-dicarboxylic anhydride (Methylnorbonene-2,3-Dicarboxylic Anhydride), 4,4 '-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] diphthalic anhydride (4,4'-[2, 2,2-Trifluoro-1- (Trifluoromethyl) Ethylidene] Diphthalic Anhydride, 4,4'-Oxydiphthalic Anhydride (4,4'-Oxydiphthalic Anhydride) and Ethylene Glycol Residue of acid 2 anhydride selected from Bis (Anhydro Trimelitate) There.

Such a compound represented by the formula (1) is preferred for improving the heat resistance, sensitivity, coating properties of the formed pattern is formed of 5 to 80% by weight of the total resin composition.

(2) polyfunctional monomers

Specific examples of the polyfunctional monomers that form the photoresist image by light include propylene glycol methacrylate, dipentaerythritol hexaacrylate, dipentaerythritol acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol acrylate tetraethylene glycol methacrylate, bisphenoxy ethyl alcohol diacrylate, trishydroxyethyl isocyanurate trimethacrylate, trimethylpropane It may be one or a mixture of two or more selected from the group consisting of trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and dipentaerythritol hexamethacrylate.

The content is 0.1 to 99 parts by weight based on 100 parts by weight of the compound represented by the formula (1) is cross-linked due to the radical reaction of the photoinitiator by UV due to the pattern formation and the binding strength of the pigment and particle components is increased to increase the optical density It is preferable at the point.

(3) silicone compound

The silicone compound is included in the resin black matrix to improve chemical resistance, heat resistance, and adhesion to chemical substances such as water, alkali, acid, and organic solvent, and specifically, phenol novolac type epoxy acrylate and bisphenol. It may be at least one compound having an epoxy group such as A type acrylate, bisphenol S type acrylate, cresol novolac type epoxy acrylate.

The content is preferably 0.1 to 80 parts by weight based on 100 parts by weight of the compound represented by Formula 1 in improving heat resistance, chemical resistance, and adhesion after pattern formation.

(4) photopolymerization initiator or photosensitizer

The photoinitiator or the photosensitizer is 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) which is an oxime ester compound. [9-ethyl-6- (2-methybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)), 1,2-octanedione-1 [(4-phenylthio) phenyl] -2 -Benzoyl-oxime (1,2-octanedione-1 [(4-phenylthio) phenyl] -2-benzoyl-oxime) with thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, Benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-petylacetophenone, p- Methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propane, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl)- Butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1- Ketones such as hydroxycyclohexylphenyl ketone; Quinones such as anthraquinone and 1,4-naphthoquinone; 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorophenyl) -s-triazine, 1,3-bis (trichloro Halogen compounds such as rophenyl) -s-triazine, phenacyl chloride, tribromomethyl phenylsulfone and tris (trichloromethyl) -s-triazine; Peroxides such as di-t-butyl peroxide; It may be selected from acyl phosphine oxides, such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.

Such a photopolymerization initiator or a photosensitizer is preferably included in 0.01 to 20 parts by weight based on 100 parts by weight of the compound represented by the formula (1).

(5) Black Pigment

As the black pigment, various inorganic oxide pigments such as carbon black, titanium black, aniline black, perylene black, strontium titanate, chromium oxide, and ceria can be used. Carbon black is preferably used, for example, CF Black EX-3276, CF Black EX-3277 series from Mikuni Color Japan, Diagram Block II, Diagram Block N339, Diagram Block SH, Diagram Block H, Diagram Block LH from Mitsubishi Japan. , Diagram block HA, diagram block SF, and the like can be used. Regal 250T, Regal 99R, Elftex 12, Raven 880 Ultra, Raven 860 Ultra, Raven 850 Ultra, Raven 790 Ultra, Raven 760 Ultra, Raven 520 Ultra, Raven 500 Ultra, etc. Can be used.

It is preferable to adjust the particle size of the black pigment to 50 to 150nm, more preferably to 80 to 100nm, which gives fluidity during spin type and spinless type coating, and after prebaking This is because it is effective for preventing surface residues and protrusions, and effective for optical density and substrate adhesion.

The black pigment is used in an amount corresponding to 1 to 90% by weight of the total composition.

(6) solvent

The solvent is propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl glycol methyl acetate, ethyl ethoxy propio Nate, methylethoxy propionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethylformamide, N, N`-dimethylacetamide, N-methylpyrrolidinone, dipropylene glycol methyl It can be selected from ether, toluene, methyl cellosolve and ethyl cellosolve.

(7) additive

The photosensitive resin composition for the resin black matrix according to the present invention may further include an additive as necessary. Examples of the additive include a silane coupling agent that improves adhesion between the black matrix and the coating substrate, and the contact angle of the coated surface. Surfactant for improving the characteristics, such as the improvement and residue improvement, etc. are mentioned.

It is effective that the resin black matrix obtained by carrying out dispersion preparation of the photosensitive resin composition which has such a composition is 1-5 cps. This is because it provides various product grades for spin type or spinless type coatings, and is more advantageous in controlling the thickness of the thin film as well as preventing residues and projections in the thin film after coating.

Moreover, the optical density of 3.0-6.0 per unit thickness (micrometer) of the pattern obtained through coating and exposing and developing the resin black matrix obtained by disperse | distributing such photosensitive resin composition is satisfy | filled.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

Synthesis Example 1 Preparation of Compound Represented by Chemical Formula 1

To a 1 L four-necked flask, 232 g of a bisphenol fluorene type epoxy compound (Formula 2) and 72 g of acrylic acid (Formula 3) were mixed with propylene glycol methyl ether acetate (PGMEA) as a solvent, and 4.56 g of triethylamine and 100 mg of hydroquinone were added thereto. The reaction is carried out while the temperature is raised to 100 ° C and maintained. At this time, nitrogen was adjusted to 10mL / min. The acid value was measured every hour, and reaction was continued until the acid value became 3.0 mgKOH / g or less, and the bisphenol fluorene type compound (formula 4) containing acrylic acid was obtained.

Next, 0.05 mol of cis-1,2,3,6-tetrahydrophthalic anhydride (cis-1,2,3,6-tetrahydrophtahlic anhydride) is added to 0.05 mol of the compound obtained by the above reaction (Formula 4) as an acid anhydride. The temperature is gradually raised to 120 ° C. After the temperature was raised to 120 ° C. and reacted for 4 hours, 0.025 mol of epoxy acrylate (Formula 5) was added to make a multi-functional group, followed by reaction at 120 ° C. for 4 hours to obtain a polyfunctional resin compound represented by Chemical Formula 6.

Synthesis Example 2

After preparing the compound represented by the formula (4) in the same manner as in Example 1, biphenyl tetracarboxylic dianhydride 90 as cis-1,2,3,6-tetrahydrophthalic anhydride, acid 2 anhydride as an acid anhydride: It was used in a 10 molar ratio to obtain a compound represented by the formula (7).

Wherein m: n is 90/10 molar ratio.

Synthesis Example 3

The compound was prepared in the same manner as in Synthesis example 2, except that an acid anhydride and an acid anhydride were used in a 10:90 molar ratio to obtain a compound having m: n of 10/90 in Chemical Formula 7.

Synthesis Example 4

The compound was prepared in the same manner as in Synthesis example 2, except that an acid anhydride and an acid anhydride were used in a 70:30 molar ratio to obtain a compound having m: n of 70/30 in Chemical Formula 7.

Synthesis Example 5

Prepared in the same manner as in Synthesis Example 2 except using an acid anhydride and an acid anhydride in a 50:50 molar ratio to obtain a compound having m: n in the formula (7) 50/50.

Synthesis Example 6

The compound was prepared in the same manner as in Synthesis example 2, except using acid 2 anhydride instead of acid anhydride to obtain a compound having m: n of 0/100 in Formula 7.

Comparative Example 1

231 g (epoxy equivalent 231) of bisphenol fluorene type epoxy resin, 450 mg of triethylbenzyl ammonium chloride, 100 mg of 2,6- diisobutyl phenol, and 72.0 g of acrylic acid were mixed, and air was mixed into a 500 ml four-necked flask. Was melted by heating to 90-100 ° C. while blowing at a rate of 25 ml per minute. The solution gradually became pale white as it was heated, but the temperature was gradually raised to 120 ° C. and completely dissolved. At this time, the solution gradually became clear and sticky, and continued stirring. The acid value was measured at intervals and the stirring was continued until the acid value was less than 2.0 mgKOH / g. It took eight hours for the acid value to reach its target (acid value 0.8).

Thereafter, the mixture was cooled to room temperature to obtain a colorless transparent solid bisphenol fluorene type epoxy acrylate.

303 g of the bisphenol fluorene type epoxy acrylate thus obtained was dissolved in 2 kg of cellosolve acetate to make a solution, and then 1,2,3,6-tetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride and Tetraethylammonium bromide 1g was added, it heated gradually, it was made to react at 110-115 degreeC for 2 hours, and the polymeric unsaturated compound represented by General formula (8) was obtained. At this time, the molar ratio of 1,2,3,6-tetrahydrophthalic anhydride and biphenyl tetracarboxylic dianhydride was 100/0.

In the above formula, the ratio of m: n is a compound of 100/0.

Comparative Example 2

In Chemical Formula 8 of Comparative Synthesis Example 1, a compound having a ratio of m: n of 90/10 was prepared.

Comparative Example 3

In Chemical Formula 8 of Comparative Synthesis Example 1, a compound having a ratio of m: n of 10/90 was prepared.

Comparative Example 4

In Chemical Formula 8 of Comparative Synthesis Example 1, a compound having a ratio of m: n of 70/30 was prepared.

Comparative Example 5

In Chemical Formula 8 of Comparative Synthesis Example 1, a compound having a ratio of m: n of 50/50 was prepared.

Comparative Example 6

In Chemical Formula 8 of Comparative Example 1, a compound having a ratio of m: n of 0/100 was prepared.

<Examples 1-6 and Comparative Examples 1-6>

Including each of the resins obtained according to Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 6, a photosensitive resin composition was prepared in the composition shown in Table 1 below.

Resin component Polyfunctional monomer Silane Epoxy Compound Photoinitiator Pigment Ingredients menstruum additive Viscosity (cps) Example One Synthesis Example 1 DPHA Bisphenol A type  OXE-02 Carbon black PGMEA GPTMS 3.5 2 Synthesis Example 2 3.5 3 Synthesis Example 3 3.6 4 Synthesis Example 4 3.5 5 Synthesis Example 5 3.6 6 Synthesis Example 6 3.7 Comparative Example One Comparative Synthesis Example 1 3.6 2 Comparative Synthesis Example 2 3.6 3 Comparative Synthesis Example 3 3.7 4 Comparative Synthesis Example 4 3.8 5 Comparative Synthesis Example 5 3.7 6 Comparative Synthesis Example 6 3.8 Resin component: 20 weight% DPHA: dipentaerythritol hexaacrylate in the total composition, 10 parts by weight based on the resin component Silane-based epoxy compound: 5 parts by weight based on the resin component Photoinitiator: 10 weight based on the resin component Sub carbon black: Particle size 90 nm to 110 nm, 10% by weight of the total resin composition, PGMEA: Propylene glycol methyl ether acetate GPTMS: Glycidoxy propyltrimethoxy silane (Shin-Etsu Co., Ltd.), 600 ppm of the total resin composition

The heat resistance, coating uniformity, development pattern stability, optical density, adhesive strength, sensitivity, and the like of the photosensitive resin compositions prepared according to the Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

(1) heat resistance

 The heat resistance was evaluated by performing a coating-prebaking-exposure-development process (exposure amount 100mJ / cm 2) on the glass substrate of the resin black matrix and comparing the shapes of the patterns before and after the postbaking process. Postbaking was performed for 40 minutes at 250 ° C. in a convection oven. Changes in the shape and thickness of the pattern were confirmed by optical microscopy and α-Step.

(2) Coating uniformity

The coating uniformity was evaluated by coating the resin black matrix on a glass substrate by coating-prebaking-exposure-developing-postbaking, and then selecting any ten places of the substrate and measuring the thickness thereof.

(T _max -T _min ) / (T _max + T _min ) X 100

Where T _max is the maximum thickness and T _min is the minimum thickness.

(3) pattern stability

The pattern stability was evaluated by vertically cutting the glass plate on which the pattern was formed and observing the cross section by SEM to confirm the degree of decrease of the film.

(4) optical density

Optical density was measured by coating a resin black matrix at about 1.0 μm, forming a pattern by an exposure-developing process, and then using Shimadzu Electronics PMT equipment.

(5) adhesive strength

Adhesive strength was measured by the ASTM D3359 (Cross Cutting Tape Test) test method after coating the resin black matrix on the glass plate.

(6) sensitivity

The sensitivity was determined by varying the exposure amount on the glass plate coated with the resin black matrix to form an exposure pattern, followed by the development-post bake process, and then determining the degree of pattern formation to determine the appropriate exposure amount.

Heat resistance Coating Uniformity (%) Pattern stability Optical density (/ ㎛) Adhesive strength Sensitivity (mJ / ㎠) Example 1 Good 2.21% Good 4.61 5B 30 Example 2 Good 2.12% Good 4.50 5B 30 Example 3 Good 2.20% Good 4.55 5B 30 Example 4 Good 2.30% Good 4.45 5B 30 Example 5 Good 2.15% Good 4.46 5B 30 Example 6 Good 2.30% Good 4.52 5B 30 Comparative Example 1 Inadequate 3.58% Bad 4.51 4B 40 Comparative Example 2 Inadequate 3.96% Bad 4.53 3B 40 Comparative Example 3 Good 3.78% Good 4.49 4B 40 Comparative Example 4 Inadequate 3.91% Bad 4.52 4B 50 Comparative Example 5 Inadequate 4.35% Good 4.47 3B 40 Comparative Example 6 Good 3.81% Bad 4.51 4B 50

From the results of Table 2, in the case of Examples 1 to 6 it can be seen that the sensitivity is particularly improved compared to Comparative Examples 1 to 6 and the coating uniformity is also improved by the improvement of the development margin. In addition, excellent results were found in pattern stability, adhesive strength, and the like.

This is judged to be the result of using a resin having increased functional groups compared to the binder resins used in Comparative Examples 1 to 6.

Claims (12)

Next, the photosensitive resin composition for resin black matrices containing a compound having an acrylate polyfunctional group in the main chain represented by the formula (1). Formula 1

Wherein R1 and R2 are the same as or different from each other, and are a hydrogen atom or a methyl group, Y is a residue of an acid anhydride, Z represents a residue of an acid anhydride, and m: n is a molar ratio of 100: 0 to 0: 100. Ratio. (A) 100 parts by weight of a compound having an acrylate polyfunctional group in the main chain represented by the following formula (1); (B) 0.1 to 99 parts by weight of a multifunctional monomer; (C) 0.1 to 80 parts by weight of a silicone compound containing an epoxy group; (D) 0.01 to 20 parts by weight of the photopolymerization initiator or the photosensitizer; (E) pigment component; And (F) Photosensitive resin composition for resin black matrices containing a solvent. Formula 1

Wherein R1 and R2 are the same as or different from each other, and are a hydrogen atom or a methyl group, Y is a residue of an acid anhydride, Z represents a residue of an acid anhydride, and m: n is a molar ratio of 100: 0 to 0: 100. Ratio. The compound represented by the formula (1) according to claim 1 or 2, wherein R1 is all hydrogen, Y is maleic anhydride, Succinic anhydride, cis-1,2,3,6-tetra Hydrophthalic anhydride (cis-1,2,3,6-Tetrahydrophthalic Anhydride), 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-Tetrahydrophthalic Anhydride), phthalic anhydride (Phthalic Anhydride) Itaconic anhydride, 1,2,4-Benzenetricarboxylic Anhydride, Methyl-Tetrahydrophthalic Anhydride, Citraconic Anhydride , 2,3-dimethylmaleic anhydride, 1-cyclopentene-1,2, -dicarboxylic anhydride, 1-Cyclopentene-1,2-Dicarboxylic anhydride, cis (5-norbornene- Endo-2,3-dicarboxylic anhydride (cis-5-Norbonene-endo-2,3-Dicarboxylic Anhydride) and 1,8-naphtanic anhydride (1,8-Naphthalic An It is a residue of an acid anhydride selected from the acid anhydride selected from hydride). Photosensitive resin composition for resin black matrices characterized by the above-mentioned. The compound represented by the formula (1) according to claim 1 or 2, wherein R1 is all hydrogen, Z is 1,2,4,5-benzenetetracarboxylic dianhydride (1,2,4,5-Bezenetetracarboxylic Dianhydride) , 4,4'-Biphthalic Dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (3,3', 4,4'-Benzophenonetetracarboxylic Dianhydride) , Pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride (1,4,5,8-Naphthalenetetracarboxylic Dianhydride), 1,2,4,5-tetracarboxylic anhydride (1 , 2,4,5-Tetracarboxylic Anhydide, Methylnorbonene-2,3-Dicarboxylic Anhydride, 4,4 '-[2,2,2-Trifluoro-1 -(Trifluoromethyl) ethylidene] diphthalic anhydride (4,4 '-[2,2,2-Trifluoro-1- (Trifluoromethyl) Ethylidene] Diphthalic Anhydride), 4,4'-oxydiphthalic anhydride (4 , 4`-Oxydiphthalic Anhydride) and ethylene glycol bis (anhydro trimellite) Agent) (Ethylene Glycol Bis (Anhydro Trimelitate)) resin, characterized in that the residue of the acid dianhydride selected from the photosensitive resin composition for a black matrix. The resin black matrix according to claim 1 or 2, wherein the compound represented by the formula (1) has a ratio of m: n, which is a molar ratio of acid anhydride and acid 2 anhydride, in a range of 100/0 to 50/50. Photosensitive resin composition for. The resin black matrix according to claim 1 or 2, wherein the compound represented by the formula (1) has a ratio of m: n, which is a molar ratio of acid anhydride and acid 2 anhydride, in the range of 100/0 to 70/30. Photosensitive resin composition for. The resin black matrix according to claim 1 or 2, wherein the compound represented by the formula (1) has a ratio of m: n, which is a molar ratio of acid anhydride and acid 2 anhydride, in a range of 0/100 to 50/50. Photosensitive resin composition for. The photosensitive resin composition for a resin black matrix according to claim 1 or 2, wherein the compound represented by the formula (1) is contained in an amount of 5 to 80% by weight in the total resin composition. The photosensitive resin composition for a resin black matrix according to claim 2, wherein the pigment component (E) is carbon black having a particle size of 50 to 150 nm. 10. The photosensitive resin composition for resin black matrix according to claim 2 or 9, wherein (E) the pigment component is contained at 1 to 90% by weight in the total resin composition. The resin black matrix which exists in the range of the viscosity of 1-5 cps obtained by carrying out dispersion preparation of the composition of Claim 1 or 2. A resin black matrix having an optical density of 3.0 to 6.0 per unit thickness in a pattern formed by photolithography after dispersion preparation and coating of the composition of claim 1 or 2.