TWI665520B - Colored photosensitive composition, colored spacer, color filter, and liquid crystal display - Google Patents

Abstract

An object of the present invention is to provide a coloring photosensitive composition which, in a method for forming a coloring spacer having different heights at one time by a photolithography method, not only ensures a voltage retention ratio of a liquid crystal, but also a required shape. Formation, step control, and adhesion to the substrate are excellent. The present invention relates to a coloring photosensitive composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) A dispersant, and used to form colored spacers of different heights at one time by a photolithography method.

Description

   Colored photosensitive composition, colored spacer, color filter and liquid crystal display device   

The present invention relates to a colored photosensitive composition and the like. More specifically, the present invention relates to a coloring photosensitive composition which can be preferably used for a coloring spacer and the like in a color filter such as a liquid crystal display, and a coloring interval formed by the coloring photosensitive composition. Components, color filters, liquid crystal display devices.

Liquid crystal displays (LCDs) use the property of switching the arrangement of liquid crystal molecules by turning on and off the voltage applied to the liquid crystal. On the other hand, the various components forming the unit of the LCD are often formed using a photosensitive composition represented by photolithography. For reasons such as easy formation of a fine structure and easier handling of a substrate for a large screen, the application range of the photosensitive composition will tend to be further expanded in the future.

However, in the LCD using the photosensitive composition, due to the electrical characteristics of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition, the voltage applied to the liquid crystal is not maintained, resulting in display unevenness of the display. problem. Especially in a member near a liquid crystal layer in a color liquid crystal display device, for example, in a liquid crystal panel, a distance between two substrates is kept constant, that is, a so-called columnar spacer, a photosensitive spacer, etc., which has a great influence. .

Previously, when a spacer was used for a TFT (Thin Film Transistor) type LCD, there was a case where a TFT as a switching element failed due to light incident on the TFT. To prevent this, for example, Patent Literature 1 describes that the spacer is made light-shielding.

In addition, in recent years, when a spacer is manufactured by a photolithography method, a method of forming spacers having different heights at one time has been proposed as the structure of the panel changes. Patent Document 2 discloses that by controlling the exposure amount and the residual film rate, the shape and step of the spacers having different heights can be realized.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 8-234212

Patent Document 2: Japanese Patent Laid-Open No. 2009-31778

However, as described in Patent Document 1, in order to make the spacer light-shielding, it is generally considered to add a pigment-containing coloring agent or the like to the photosensitive composition. In the case where the hardenability of the spacer layer is reduced and the influence of impurities derived from the pigment, etc., the electrical characteristics may be impaired.

In addition, Patent Document 2 relates to a spacer without adding a pigment, and it can be found that when applied to the primary formation of a colored spacer with a pigment added, the pigment absorbs light in an ultraviolet region that contributes to photopolymerization, and therefore, it is in the opening portion. In a pattern with a small light transmittance, the hardenability is poor, and it is difficult to achieve the characteristics of the spacers with different heights, the control of the step difference, and the adhesion with the substrate.

The present invention has been made in view of such circumstances. That is, the main object of the present invention is to provide a coloring photosensitive composition which, in a method for forming a coloring spacer having different heights at one time by a photolithography method, not only ensures the voltage retention of the liquid crystal, but also The required shape formation, step control, and adhesion to the substrate are also excellent.

Another object of the present invention is to provide a colored spacer formed by such a colored photosensitive composition.

Furthermore, another object of the present invention is to provide a color filter including such a coloring spacer.

Furthermore, another object of the present invention is to provide a liquid crystal display device including such a color filter.

Furthermore, another object of the present invention is to provide a method of using such a coloring photosensitive composition and forming a coloring spacer having different heights at one time by a photolithography method.

The present inventors conducted intensive research on the above problems, and found that by using a specific alkali-soluble resin and a dispersant, the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound and the content of the specific alkali-soluble resin Setting the ratio to a specific range can solve the above problems and complete the present invention. That is, the gist of this invention is as follows.

[1] A coloring photosensitive composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and ( f) a dispersant for forming colored spacers of different heights by photolithography at one time; and containing at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2) Or (b) an alkali-soluble resin; an acrylic block copolymer containing a nitrogen atom as (f) a dispersant; (b) the weight ratio of the alkali-soluble resin to (d) the ethylenically unsaturated compound is less than 7; The ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 12% by weight or more;

     <Alkali-soluble resin (A-1)>     

A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polybasic acid anhydride;

     <Alkali soluble resin (A-2)>     

A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polyhydric alcohol and a polyacid anhydride.

[2] The colored photosensitive composition according to the above [1], wherein the ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20% by weight or more.

[3] The colored photosensitive composition according to the above [1] or [2], wherein (a) the content ratio of the colorant is less than 30% by weight based on the total solid content in the colored photosensitive composition.

[4] The colored photosensitive composition according to any one of the above [1] to [3], wherein (a) the content ratio of the colorant is 25% by weight or more with respect to the total solid content in the colored photosensitive composition.

[5] The colored photosensitive composition according to any one of the above [1] to [4], which contains one of the following (1) a red pigment, and one of the following (2) a blue pigment and the following (3) a purple pigment At least one as (a) a colorant; (1) a red pigment selected from CI Pigment Red 177, 254; (2) a CI Pigment Blue 15: 6 blue pigment; (3) as a CI Pigment Violet 23 Purple pigment.

[6] The colored photosensitive composition according to any one of the above [1] to [4], which contains C.I. Pigment Red 254 and C.I. Pigment Blue 15: 6 as (a) a colorant.

[7] The colored photosensitive composition according to any one of the above [1] to [6], which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB The block copolymer and the BAB block copolymer include an A block having at least one of a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and amine group.

[8] The colored photosensitive composition according to any one of the above [1] to [6], which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB The block copolymer and the BAB block copolymer include an A block having a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and an amine group.

[9] The colored photosensitive composition according to any one of the above [1] to [6], which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB The block copolymer and the BAB block copolymer include an A block having an amine group without a quaternary ammonium salt group in the side chain, and a B block having no quaternary ammonium salt group and an amine group at the side chain.

[10] The coloring photosensitive composition according to any one of the above [1] to [9], which contains an oxime ester compound as (c) a photopolymerization initiator.

[11] A coloring spacer formed by the coloring photosensitive composition as described in any one of the above [1] to [10] at one time and having different heights.

[12] A color filter including the coloring spacer according to the above [11].

[13] A liquid crystal display device including the color filter according to the above [12].

[14] A method for forming a colored spacer, using the colored photosensitive composition according to any one of the above [1] to [10], and forming colored spacers of different heights at one time by a photolithography method.

According to the present invention, in a method for forming colored spacers of different heights at one time by a photolithography method, not only the voltage retention of the liquid crystal is ensured, but also the formation of a desired shape, the control of the step difference, and the The tightness of the substrate.

1‧‧‧Colored spacer pattern

2‧‧‧ glass substrate

3‧‧‧ bottom bracket

4‧‧‧ section

41‧‧‧Pattern side

A, A'‧‧‧ intersection

H‧‧‧Pattern height

L‧‧‧ bottom section diameter

1 (A) and 1 (B) are diagrams for explaining the shape of a substantially cylindrical spacer pattern of the embodiment, FIG. 1 (A) is a plan view of the spacer pattern, and FIG. 1 (B) is a spacer pattern Section view.

The following is a detailed description of the form for implementing the present invention. The description of the constituent elements described below is an example (representative example) of the embodiment of the present invention. The present invention is not particularly limited as long as it does not exceed its gist. Such content.

In addition, in the present invention, "(meth) acrylic acid" means both acrylic acid and methacrylic acid, and (meth) acrylic acid group, (meth) acrylic acid ester, (meth) acrylic acid, etc. Have the same meaning; the so-called "(co) polymer" means including both homopolymer and copolymer; so-called "(acid) anhydride", "(anhydrous) ... acid", It is meant to include both acids and their anhydrides.

In addition, in the present invention, the "monomer" refers to the meaning of a so-called high molecular substance, and includes dimers, trimers, oligomers, and the like in addition to monomers in the narrow sense. Here, the "total solid content" means the total of all components other than the solvent contained in the coloring photosensitive composition of this invention.

[1] One-time forming method of colored spacers with different heights

The method for forming colored spacers of different heights by photolithography at one time is mainly characterized by an exposure mask in the exposure step.

It is known to use an exposure mask having a light-shielding layer that shields light from penetrating and several openings that allow light to pass through, and the average light transmittance of one of the openings is smaller than the average light transmittance of other openings as the exposure. Photomask method. This method uses an opening having a light-shielding layer (light transmittance 0%) and several openings, and having the highest average light transmittance relative to the average light transmittance (usually 100% light transmittance; hereinafter referred to as full penetration) Opening portion) An exposure mask having a small opening portion (average light transmittance exceeding 0% and less than 100%; preferably more than 5% and less than 50%; hereinafter referred to as an intermediate penetration opening portion). According to this method, for example, in the case of a negative-type colored photosensitive composition, a pattern formed is generated by a difference in average light transmittance between a middle penetrating opening portion and a completely penetrating opening portion, that is, a difference in exposure amount. The difference in the degree of hardening can be formed by development and thermal curing, so that colored spacers of different heights can be formed.

[2] Colored photosensitive composition

The colored photosensitive composition of the present invention contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersion. And is used to form colored spacers of different heights at one time by photolithography; characterized in that it contains at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2) As (b) an alkali-soluble resin; containing an acrylic block copolymer containing a nitrogen atom as (f) a dispersant; (b) the weight ratio of the alkali-soluble resin to (d) the ethylenically unsaturated compound is less than 7; and The ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 12% by weight or more.

    <Alkali-soluble resin (A-1)>    

A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting with a polybasic acid anhydride.

    <Alkali soluble resin (A-2)>    

A resin obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and further reacting with a polyhydric alcohol and a polyacid anhydride.

[2-1] (a) Colorant

Pigments can often be used as colorants. As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment, and black pigment can be used. In addition, as the structure, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, In addition to organic pigments such as system-based, indanthrene-based, and osmium-based, various inorganic pigments can also be used. Specific examples of pigments that can be used are exemplified by pigment numbers. The terms "CI Pigment Red 2" and the like listed below mean the color index (CI).

Examples of the red pigment include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38 , 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1 , 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1 , 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146 , 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202 , 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250 , 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among them, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254 is preferable, and C.I. Pigment Red 177, 209, 224, 254 is more preferable.

Examples of the blue pigment include CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among them, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 are preferable, and C.I. Pigment Blue 15: 6 is more preferable.

Examples of the green pigment include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among these, C.I. Pigment Green 7, 36 is preferable.

Examples of the yellow pigment include CI Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35 : 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83 , 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134 , 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170 , 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199 , 200, 202, 203, 204, 205, 206, 207, 208. Among them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 is preferable, and C.I. Pigment Yellow 83, 138, 139, 150, 180 is more preferable.

Examples of the orange pigment include CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61 , 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, C.I. pigment oranges 38 and 71 are preferable. Examples of the purple pigment include CI Pigment Violet 1, 1: 1,2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27 , 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, C.I. Pigment Violet 19 and 23 are preferred, and C.I. Pigment Violet 23 is further preferred.

Examples of the black pigment include black (BASF K0084, K0086), cyan black, and black HB (C.I.26150).

In the coloring photosensitive composition of the present invention, a single black colorant may be used, or a black colorant produced by a mixture of red, green, blue, and the like may be used. These black pigments can be appropriately selected from inorganic or organic pigments and dyes such as carbon black and titanium black, and can be used alone or in combination.

Examples of commercially available products of carbon black include the following trademarks.

Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900, etc.

Made by Degussa: Printex95, Printex90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, etc.

Manufactured by Cabot: Monarch460, Monarch430, Monarch280, Monarch120, Monarch800, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACKPEARLS480, PEARLS130.

Manufactured by Columbian Carbon: RAVEN11, RAVEN15, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, etc.

Examples of commercially available products of titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, and the like manufactured by Mitsubishi Materials.

From the viewpoint of light-shielding property, the colored photosensitive composition of the present invention preferably contains at least one of the following red pigments (1), and the blue pigments (2) and the purple pigments (3) below. Or (a) a colorant.

(1) Red pigment selected from C.I. Pigment Red 177, 254

(2) As a blue pigment of C.I. Pigment Blue 15: 6

(3) Purple pigment as C.I.Pigment Violet 23

Among these, (1) and (2) are preferred from the viewpoints of ensuring the voltage retention of the liquid crystal, controlling the step, and the adhesion to the substrate. From the viewpoint of improving the light-shielding property in the visible light region, it is preferable to contain C.I. Pigment Red 254 and C.I. Pigment Blue 15: 6.

In the colored photosensitive composition of the present invention, the content ratio of (a) the coloring agent is preferably 35% by weight or less, and more preferably less than 30% by weight, relative to the total solid content of the colored photosensitive composition. If it is 35% by weight or less, the difference (ΔH) between the height of the colored spacer pattern completely penetrating the opening portion and the height of the colored spacer pattern penetrating the middle opening portion is large, which is preferable. If it is less than 30% by weight, the difference (ΔH) between the height of the colored spacer pattern completely penetrating the opening portion and the height of the colored spacer pattern penetrating the opening portion exceeds 0.35 μm. A preferred range is from 5 to 28% by weight, and even more preferably from 10 to 25% by weight. If (a) the content ratio of the colorant is too large, the sensitivity of the coloring photosensitive composition may be lowered, and the shapes and steps of the spacers having different heights may not be formed. On the other hand, when the content ratio of the colorant is too small, there may be cases where sufficient light-shielding properties as a colored spacer cannot be secured.

[2-2] (b) Alkali-soluble resin

The alkali-soluble resin (A-1) used in the present invention is obtained by adding an α, β-unsaturated monocarboxylic acid or an ester portion having an carboxyl group to an epoxy resin by an method such as: The monocarboxylic acid ester reacts with a polybasic acid anhydride to impart alkali solubility. The reaction product has substantially no epoxy group in chemical structure.

As the epoxy resin used as a raw material, a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a triphenol methane type can be preferably used. Epoxy resin, biphenol novolac epoxy resin, naphthol novolac epoxy resin, epoxy resin as a reaction product of the addition polymerization reaction product of dicyclopentadiene and phenol or cresol and epihalohydrin, Adamantyl-containing epoxy resin, fluorene type epoxy resin, etc.

The molecular weight of the epoxy resin is measured by gel permeation chromatography (GPC, Gel Permeation Chromatography), and is set to a polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw"). The Mw is usually 200 to 200,000. The range is preferably in the range of 300 to 100,000. When the molecular weight is less than the above range, there may be cases where it is not easy to obtain a better Mw alkali-soluble resin (A-1). On the other hand, when the molecular weight exceeds the above range, it may be caused by α, β-unsaturated monocarboxylic acid. During the addition reaction, gelation is likely to occur or production may become difficult.

Examples of the α, β-unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, itaconic acid, butenoic acid, and cinnamic acid. Acrylic acid and methacrylic acid are preferred, and acrylic acid is more reactive due to its reactivity. good. Examples of the α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion include 2-butadioxyethyl acrylate, 2-cis-butenedimethoxyethyl acrylate, and 2-acrylate -Phthalic acid ethyl ester, 2-hexahydrophthalic acid ethyl acrylate, 2-butadimethoxy ethyl methacrylate, 2-cis butene methacrylate Dimethoxyethyl, 2-phthalicyloxyethyl methacrylate, 2-hexahydrophthalicyloxyethyl methacrylate, 2-butanefluoric acid butenoic acid Oxyethyl and the like.

The addition reaction of an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an ester portion and an epoxy resin can be performed by a known method. The amount of the α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the raw material epoxy resin. The range is more preferably in the range of 0.7 to 1.1 equivalents. If the amount of α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic ester having a carboxyl group in the ester portion is small, the introduction amount of unsaturated group is insufficient, and the subsequent reaction with polybasic acid anhydride is also Inadequate situation. It is also disadvantageous that a large amount of epoxy groups remain. On the other hand, when this amount is large, there may be cases where α, β-unsaturated monocarboxylic acid or an ester thereof remains as an unreacted substance. In either case, there is a possibility that the hardening characteristics of the coating film are deteriorated.

Furthermore, in the present invention, if the final resin structure is the same even if the epoxy resin is not used in the manufacturing steps, it is also defined as belonging to the category of alkali-soluble resin (A-1) in this application. Examples thereof include a method of reacting a novolac resin with an unsaturated group-containing epoxy compound.

Examples of the polybasic acid anhydride added to the product obtained by adding an epoxy resin to an α, β-unsaturated monocarboxylic acid or an ester portion having a carboxyl group include α, β-unsaturated monocarboxylic acid, and maleic anhydride Diacid anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, diphenylketone tetracarboxylic dianhydride, formic acid Hexahydrophthalic anhydride, internal methylenetetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc. Acid anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, particularly preferred compounds It is tetrahydrophthalic anhydride and biphenyltetracarboxylic dianhydride.

Regarding the addition reaction of a polybasic acid anhydride, a known method can also be used. The addition amount of the polybasic acid anhydride is preferably such that the acid value of the resulting epoxy acrylate resin is in a range of 10 mgKOH / g to 150 mgKOH / g, and more preferably in a range of 20 mgKOH / g to 140 mgKOH / g. If the acid value is less than the above range, the alkali developability will be insufficient, and if it exceeds the above range, the tendency of the hardening performance to be deteriorated will be observed.

The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (A-1) used in the present invention measured by gel permeation chromatography (GPC) is usually 1,500 or more, preferably 2,000 or more, and usually It is 50,000 or less, preferably 30,000 or less, and more preferably 10,000 or less. If the weight-average molecular weight of the alkali-soluble resin (A-1) is too small, the sensitivity tends to decrease. If the weight-average molecular weight is too large, the solubility in the developing solution may be insufficient, which is not preferable.

The alkali-soluble resin (A-2) used in the present invention is obtained by adding an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having an carboxyl group to an epoxy resin, and then Polyol and polyanhydride are obtained by reaction.

All the synthesis methods used for the synthesis of the alkali-soluble resin (A-1) or the components other than the polyol can be used for the synthesis of the alkali-soluble resin (A-2). The alkali-soluble resin (A-2) is usually mixed by reacting an epoxy resin with an α, β-unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in an ester portion. Polyols and polyanhydrides are obtained by heating. In this case, the mixing order of the polyol and the polyacid anhydride is not particularly limited.

As the polyhydric alcohol used in the synthesis of the alkali-soluble resin (A-2), for example, it is preferably selected from the group consisting of trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1 One or two or more polyhydric alcohols in 2,3-glycerol.

By using a polyhydric alcohol, the molecular weight of the alkali-soluble resin (A-2) can be increased to introduce branches into the molecule, and the molecular weight and viscosity can be balanced. In addition, it is possible to increase the introduction rate of the acid group in the molecule and obtain a balanced organic adhesive such as sensitivity and adhesion.

If the amount of polyhydric alcohol is too small, the effect will be small, and if it is too large, there is a possibility of thickening or gelling. Therefore, it has a higher viscosity than the epoxy resin component and the α, β-unsaturated monocarboxylic acid or ester portion. The reactant of the carboxyl α, β-unsaturated monocarboxylic acid ester component is usually about 0.01 to 0.5 times the weight, preferably about 0.02 to 0.2 times the weight.

The acid value of the alkali-soluble resin (A-2) obtained in the above manner is usually 10 mgKOH / g or more, and preferably 50 mgKOH / g or more. If the acid value is less than 10 mgKOH / g, the developability may be insufficient. In addition, if the acid value is too high, the alkali resistance of the colored photosensitive composition may be problematic (that is, the pattern surface may be roughened or the film may be reduced by an alkaline developer). Therefore, the acid value is preferably 200 mgKOH. / g or less, more preferably 150 mgKOH / g or less.

The polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin (A-2) measured by gel permeation chromatography (GPC) is preferably 1,500 or more, and more preferably 2,000 or more. It is preferably 20,000 or less, and more preferably 10,000 or less. If the weight average molecular weight is too small, there may be a problem in sensitivity, coating film strength, and alkali resistance. If it is too large, problems in developability or resolubility may occur.

The total amount of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) with respect to the total solid content in the colored photosensitive composition of the present invention is 12% by weight or more, preferably 20% by weight or more, more It is preferably 30% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, and more preferably 50% by weight or less. If the ratio of the alkali-soluble resin is more than this range, the developability is lowered and the pigment ratio is too small, so there is a tendency that the necessary light-shielding property cannot be ensured. On the other hand, if it is too small, the desired The shape and step of the spacer.

As the alkali-soluble resin, an alkali-soluble resin other than the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) may be used in combination.

[2-3] (c) Photopolymerization initiator

The photopolymerization initiator of the present invention refers to a compound that can generate a radical that polymerizes an ethylenically unsaturated group by ultraviolet rays or heat.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.

2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -mesanthine , 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -mesan Isohalomethylated tris Derivatives; halomethylation Diazole derivatives; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (3'-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2 -(O-methoxyphenyl) -4,5-diphenylimidazole dimer and other imidazole derivatives; benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin and benzoin alkyl ethers Class; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone; benzoanthrone derivatives; diphenyl ketones, Michelin Ketone, 2-methyldiphenyl ketone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone, 2-carboxydiphenyl Diphenyl ketone derivatives such as phenyl ketone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α -Hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2 -Methyl- (4 '-(methylthio) phenyl) -2- Acetophenone derivatives such as phosphono-1-acetone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thia anthrone, 2-ethylthio anthrone, 2-iso Propylthiaxanthone, 2-chlorothiaxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Derivatives such as thioanthrone, such as ketones; benzoate derivatives, such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p-methyl Acridine derivatives such as acridine; 9,10-dimethylbenzophene Isorphine Derivatives; bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) bisphenyltitanium, bis (cyclopentadienyl) bis (2,3,4,5,6-penta Fluorophenyl-1-yl) titanium, bis (cyclopentadienyl) bis (2,3,5,6-tetrafluorophenyl-1-yl) titanium, bis (cyclopentadienyl) bis (2,4 , 6-trifluorophenyl-1-yl) titanium, bis (cyclopentadienyl) 2,6-bis (fluorophenyl-1-yl) titanium, bis (cyclopentadienyl) 2,4-bis ( Fluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5,6-pentafluorophenyl-1-yl) titanium, bis (methylcyclopentadienyl) ) Bis (2,6-difluorophenyl-1-yl) titanium, bis (cyclopentadienyl) 2,6-bis (fluoro-3- (py-1-yl) -benzene-1-yl) titanium Isotitanium derivatives; 2-methyl-1 [4- (methylthio) phenyl] -2- Linylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) butane-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4- Dimethylaminophenylacetone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-bis Α-Aminoalkylphenone compounds such as ethylamino-3- (4-diethylaminobenzyl) coumarin, 4- (diethylamino) chalcone; as light Polymerization initiators, particularly in terms of sensitivity, are more effective in oxime derivatives (oxime-based and ketoxime-based compounds). When using alkali-soluble resins containing phenolic hydroxyl groups, etc., in terms of sensitivity This is disadvantageous, and especially such oxime derivatives (oxime-based and ketoxime-based compounds) having excellent sensitivity are useful.

Examples of the oxime-based compound include compounds containing a structural portion represented by the following general formula (2), and preferably, an oxime ester-based compound represented by the following general formula (3).

(In the formula (2), R ² represents an alkylalkyl group having 2 to 12 carbon atoms, a heteroarylalkylalkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and carbon number, respectively, which may be substituted. 3 to 8 cycloalkanoyl groups, 3 to 20 carbon alkoxycarbonyl alkyl groups, 8 to 20 carbon phenoxy carbonyl alkyl groups, 3 to 20 carbon heteroaryloxy carbonyl groups Group, amino alkylcarbonyl group with 2 to 10 carbon atoms, arylfluorenyl group with 7 to 20 carbon atoms, heteroarylfluorenyl group with 1 to 20 carbon atoms, alkoxycarbonyl group with 2 to 10 carbon atoms, or 7 carbon number Aryloxycarbonyl group of ~ 20.)

(In formula (3), R ^1a represents hydrogen, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl alkyl group having 1 to 20 carbon atoms, and carbon number, respectively, which may be substituted. Alkoxycarbonylalkyl of 3-20, phenoxycarbonylalkyl of 8-20, heteroaryloxycarbonylalkyl or heteroarylthioalkyl of 1-20, carbon of 1-20 Amine alkyl, alkanoyl having 2 to 12 carbons, alkenyl having 3 to 25 carbons, naphthene having 3 to 8 carbons, aryl fluorenyl having 7 to 20 carbons, 1 carbon A heteroarylfluorenyl group of 20 to 20, an alkoxycarbonyl group of 2 to 10 carbons, or an aryloxycarbonyl group of 7 to 20 carbons.

R ^1b represents an arbitrary substituent including an aromatic ring or a heteroaromatic ring.

In addition, R ^1a and R ^1b may form a ring together, and examples of the linking group thereof include an alkylene group having 1 to 10 carbon atoms, a polyvinyl group (-(CH = CH) _r- ), and a polyalkylene group which may each have a substituent. An ethynyl group (-(C≡C) _r- ) or a combination of these (in addition, r is an integer of 0 to 3).

R ^2a represents an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and a cycloalkane group having 3 to 8 carbon atoms, respectively, which may be substituted. Group, alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, and 2 to 10 carbon atoms Aminocarbonyl group, arylfluorenyl group with 7 to 20 carbon atoms, heteroarylfluorenyl group with 1 to 20 carbon atoms, alkoxycarbonyl group with 2 to 10 carbon atoms or aryloxycarbonyl group with 7 to 20 carbon atoms. )

As R ^{2 in} the general formula (2) and R ^2a in the general formula (3), preferred are alkyl alkanoyl groups having 2 to 12 carbon atoms, heteroarylalkanoyl groups having 1 to 20 carbon atoms, A cycloalkanoyl group having 3 to 8 carbon atoms.

As R ^1a in the general formula (3), an unsubstituted methyl group, an ethyl group, a propyl group, or a propyl group substituted with an N-ethylfluorenyl-N-ethoxymethylamino group is preferable.

In addition, as R ^1b in the general formula (3), preferred examples include a hydrazine methyl group which may be substituted, a thia anthrone group which may be substituted, and a phenyl sulfide group which may be substituted.

Specific examples of the oxime ester compound to be used in the present invention include the compounds exemplified below, but they are not limited to these compounds.

[Chemical 3]

Examples of the ketoxime-based compound include compounds containing a structural moiety represented by the following general formula (4), and preferably an oxime ester-based compound represented by the following general formula (5).

(In the general formula (4), R ⁴ has the same meaning as R ² in the general formula (2).)

(In the general formula (5), R ^3a represents a phenyl group which may be substituted, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, Alkoxycarbonylalkyl with 3 to 20 carbon atoms, phenoxycarbonylalkyl with 8 to 20 carbon atoms, alkylthioalkyl with 2 to 20 carbon atoms, and heteroaryloxycarbonylalkane with 1 to 20 carbon atoms Or heteroarylthioalkyl, amine alkyl having 1 to 20 carbons, alkanoyl having 2 to 12 carbons, alkenyl having 3 to 25 carbons, and cycloalkyl sulfonyl having 3 to 8 carbons , Arylfluorene group with 7 to 20 carbon atoms, Heteroarylarylene group with 1 to 20 carbon atoms, Alkoxycarbonyl group with 2 to 10 carbon atoms, or Aryloxycarbonyl group with 7 to 20 carbon atoms.

R ^3b represents an arbitrary substituent including an aromatic ring or a heteroaromatic ring.

In addition, R ^3a and R ^3b may form a ring together, and examples of the linking group thereof include an alkylene group having 1 to 10 carbon atoms, a polyvinyl group (-(CH = CH) _r- ), and a polyalkylene group which may each have a substituent. An ethynyl group (-(C≡C) _r- ) or a combination of these (in addition, r is an integer of 0 to 3).

R ^4a represents an alkylfluorenyl group having 2 to 12 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, a cycloalkylfluorenyl group having 4 to 8 carbon atoms, a benzamidine group having 7 to 20 carbon atoms, Heteroarylfluorenyl with 3 to 20 carbons, alkoxycarbonyl with 2 to 10 carbons, aryloxycarbonyl with 7 to 20 carbons, heteroaryl with 2 to 20 carbons, or 2 to 20 with carbons Alkylaminocarbonyl. )

As R ^{4 in} the general formula (4) and R ^4a in the general formula (5), preferred are alkyl alkanoyl groups having 2 to 12 carbon atoms, heteroaryl alkyl fluorenyl groups having 1 to 20 carbon atoms, Cycloalkylfluorenyl groups having 3 to 8 carbon atoms, and arylfluorenyl groups having 7 to 20 carbon atoms.

As R ^3a in the general formula (5), an unsubstituted ethyl group, a propyl group, a butyl group, or an ethyl group or a propyl group substituted with a methoxycarbonyl group is preferred.

Moreover, as R <^3b> in said General formula (5), the hydrazine formyl group which can be substituted, and the phenyl sulfide group which can be substituted are mentioned preferably.

Specific examples of the ketoxime ester compound to be used in the present invention include the compounds exemplified below, but they are not limited to these compounds.

These oxime and ketoxime ester compounds are known compounds per se, for example, one of a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 and Japanese Patent Laid-Open No. 2006-36750.

These photopolymerization initiators may be used individually by 1 type, and may use 2 or more types together.

The proportion of the photopolymerization initiator in the light-shielding sexy light-sensitive resin composition of the present invention is usually 0.4 to 15% by weight, and preferably 0.5 to 10% by weight, relative to the total solid content. If the ratio of the photopolymerization initiator is too much more than this range, the developability tends to decrease. On the other hand, if the ratio is too small, it may not be possible to form a better voltage holding ratio or the shape and step of the colored spacer.

The colored photosensitive composition of the present invention is characterized in that the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is less than 7. The alkali-soluble resin in this case means the total of all alkali-soluble resins containing at least one of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2). The weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is usually 1 or more, preferably 1.5 or more, further preferably 2 or more, preferably 6 or less, and further preferably 5 or less. If it is 7 or more, a necessary step may not be formed, and if it is too small, developability may fall. When a large amount of an alkali-soluble resin having a long dissolution time with respect to a developer is used, the developability may be reduced even if it is 7 or more.

[2-4] (d) Ethylenically unsaturated compounds

The photopolymerization initiator may be used together with an ethylenically unsaturated compound.

As the ethylenically unsaturated compound used herein, it means a compound having one or more ethylenically unsaturated bonds in the molecule, in terms of polymerizability, crosslinkability, and a developing solution that can expand the exposure and non-exposure parts accompanying it. In terms of differences in solubility, a compound having two or more ethylenically unsaturated bonds in the molecule is preferred, and the (meth) acryloxy group-derived (meth) ) Acrylate compounds.

Furthermore, if a compound having three or more ethylenically unsaturated bonds in the molecule is used, it is preferable in terms of voltage retention.

Examples of the compound having one or more ethylenically unsaturated bonds in the molecule include (meth) acrylic acid, butenoic acid, methacrylic acid, maleic acid, itaconic acid, methyl maleic acid, and the like. Saturated carboxylic acids and their alkyl esters, (meth) acrylonitrile, (meth) acrylamide, styrene, and the like.

Typical examples of compounds having two or more ethylenically unsaturated bonds in the molecule include esters of unsaturated carboxylic acids and polyhydroxy compounds, phosphates containing (meth) acryloxy groups, and (meth) (Meth) acrylate urethanes of hydroxy acrylate and polyisocyanate compounds, and epoxy (meth) acrylates of (meth) acrylic or hydroxy (meth) acrylate compounds and polyepoxides Wait.

Specific examples of the esters of the unsaturated carboxylic acid and the polyhydroxy compound include the following compounds.

Reactants of unsaturated carboxylic acids and sugar alcohols: Specific examples of sugar alcohols include ethylene glycol, polyethylene glycol (addition number 2 to 14), propylene glycol, polypropylene glycol (addition number 2 to 14), 1, 3 -Propylene glycol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and the like.

Reactant of the alkylene oxide adduct of unsaturated carboxylic acid and sugar alcohol: Sugar alcohol is the same as above. Specific examples of the "alkylene oxide adduct" include an ethylene oxide adduct and a propylene oxide adduct.

Reactants of unsaturated carboxylic acids and alcohol amines; specifically, alcohol amines include diethanolamine, triethanolamine, and the like.

Specific esters of unsaturated carboxylic acids and polyhydroxy compounds are described below.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane Tris (meth) acrylate, trimethylolpropane ethylene oxide addition tris (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition Tris (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylates and the like, and the same methacrylic acid esters, methacrylic acid esters, maleic acid esters, itaconic acid esters, methyl maleic acid esters, and the like.

Examples of esters of unsaturated carboxylic acids and polyhydroxy compounds include unsaturated polycarboxylic compounds such as aromatic polyhydroxy compounds such as unsaturated carboxylic acids and hydroquinone, resorcinol, catechol, bisphenol F, and bisphenol A. , Or reactants of these ethylene oxide adducts. Specific examples include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], and the like ; Also, the reaction product of the unsaturated carboxylic acid and the heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate as mentioned above, such as tris (2-hydroxyethyl) isocyanurate Bis (meth) acrylate, tri (meth) acrylate, etc .; and examples thereof include reactants of unsaturated carboxylic acid with polycarboxylic acid and polyhydroxy compound, such as (meth) acrylic acid and phthalic acid and Condensate of ethylene glycol, (meth) acrylic acid with maleic acid and diethylene glycol, condensate of (meth) acrylic acid with terephthalic acid and pentaerythritol, (meth) acrylic acid with hexamethylene Condensates of diacid with butanediol and glycerol.

As the (meth) acryloxy group-containing phosphates, those represented by the following general formulae (6), (7), and (8) are preferred.

(In the formulae (6), (7), and (8), R ¹⁰ represents a hydrogen atom or a methyl group, p and p 'are integers of 1 to 25, and q is 1, 2, or 3.)

Here, p and p 'are preferably 1 to 10, and particularly preferably 1 to 4. Specific examples of these include, for example, (meth) acrylic acid oxyethyl phosphate and bis [(methyl) phosphate Acrylic ethoxyethyl] ester, (meth) acrylic ethoxy ethylene glycol phosphate, etc. can be used individually or as a mixture.

Examples of the (meth) acrylic acid urethanes of the (meth) acrylic hydroxy ester compound and the polyisocyanate compound include, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and tetramethylol Reactants of (meth) acrylic hydroxy ester compounds such as ethane tri (meth) acrylate and the following polyisocyanate compounds, etc .: hexamethylene diisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, etc. Aliphatic polyisocyanate, cycloaliphatic diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, dicycloheptane triisocyanate and other alicyclics Polyisocyanates such as aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanatephenyl) thiophosphate, and heterocyclic polyisocyanates such as isocyanurate.

As mentioned above, for example, trade names "U-4HA", "UA-306A", "UA-MC340H", "UA-MC340H", "U6LPA", etc. manufactured by Shin Nakamura Chemical Co., Ltd. may be mentioned.

Among these, a compound having 4 or more urethane bonds [-NH-CO-O-] and 4 or more (meth) acryl fluorenyloxy groups in one molecule is preferable, and the compound can be borrowed Compounds having four or more, preferably six or more isocyanate groups in one molecule as described below, for example, "Duranate ME20-100" manufactured by Asahi Kasei Corporation, pentaerythritol di (meth) acrylate, dipentaerythritol Tris (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like have one or more hydroxyl groups and two or more, preferably three or more (methyl groups) in one molecule ) Acrylic alkoxy compounds are obtained by reacting a compound having 4 or more, preferably 6 or more isocyanate groups in one molecule, for example, a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol, and six A compound obtained by reacting a diisocyanate compound such as methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, etc .; or two or more molecules in one molecule such as ethylene glycol Combination of hydroxyl groups With the reduction of "Duranate 24A-100" manufactured by Asahi Kasei Kogyo, "Duranate 22A-75PX" manufactured by Asahi Kasei Kogyo, "Duranate 21S-75E" manufactured by Asahi Kasei Kogyo, and "Duranate 18H-70B" manufactured by Asahi Kasei Kogyo Diurea type, "Duranate P-301-75E" manufactured by Asahi Kasei Industries, "Duranate E-402-90T" manufactured by Asahi Kasei Industries, and "Duranate E-405-80T" manufactured by Asahi Kasei Industries A compound obtained by reacting a compound having three or more isocyanate groups in one molecule; or a compound obtained by polymerizing or copolymerizing ethyl isocyanate (meth) acrylate and the like.

Examples of epoxy (meth) acrylates of (meth) acrylic acid or (meth) acrylic hydroxy ester compounds and polyepoxides include (meth) acrylic acid and (meth) acrylic acid as described above. A reactant of a hydroxy ester compound with a polyepoxide compound as described below. The polyepoxide compounds include: (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) 1 , 4-Butanediol polyglycidyl ether, (Poly) 1,5-pentanediol polyglycidyl ether, (Poly) neopentyl glycol polyglycidyl ether, (Poly) 1,6-hexanedione Aliphatic polyepoxides such as alcohol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitan polyglycidyl ether, phenol Novolac polyepoxides, brominated phenol novolac polyepoxides, (ortho, meta, p) cresol novolac polyepoxides, bisphenol A polyepoxides, bisphenol F polyepoxides, etc. Family of polyepoxides, heterocyclic polyepoxides such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl isocyanurate, etc. Wait.

Examples of other ethylenically unsaturated compounds include, in addition to the above, (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; o Vinyl-containing compounds such as diethylene phthalate; thioether-bond compounds that increase the crosslinking speed by sulfurizing the ether bonds of ethylenically unsaturated compounds containing ether bonds into thioether bonds using phosphorus pentasulfide and the like And the use of isocyanate or mercapto-containing silane coupling agents as described in Japanese Patent No. 3164407 and Japanese Patent Laid-Open No. 9-100111, etc., to make polyfunctional (meth) acrylate compounds with a particle size of 5 to 30 nm Silica sol [for example, organic silica sol dispersed by isopropanol ("IPA-ST" manufactured by Nissan Chemical Co., Ltd.), organic silica sol dispersed by methyl ethyl ketone ("MEK-ST" manufactured by Nissan Chemical Co., Ltd. ), Methyl isobutyl ketone-dispersed organosilica sol ("MIBK-ST" manufactured by Nissan Chemical Co., Ltd.), etc.), and the ethylenically unsaturated compound and silica sol are passed through a silane coupling agent. React and bond to increase Compounds such as the strength and heat resistance of hardened materials.

In the present invention, as the ethylenically unsaturated compound, ester (meth) acrylates or (meth) acrylate urethanes are preferred, and among them, dipentaerythritol hexa (meth) acrylate is particularly preferred. , Dipentaerythritol penta (meth) acrylate, etc.

Each of the above ethylenically unsaturated compounds may be used alone, or two or more of them may be used in combination.

The proportion of the ethylenically unsaturated compound in the light-shielding and sexy resin composition of the present invention is generally 1 to 60% by weight, preferably 5 to 40% by weight, and particularly preferably 12 to 30% by weight relative to the total solid content. . If the ratio of the ethylenically unsaturated compound is too much in this range, the developability tends to decrease. On the other hand, if it is too small, it tends to be difficult to ensure the voltage holding ratio or to form the shape and step of the colored spacer.

In the present invention, the ethylenically unsaturated compound does not contain the alkali-soluble resin.

[2-5] (e) Solvent

Each component contained in the coloring photosensitive composition of the present invention shown above is usually dissolved or dispersed in a solvent and used as a coloring photosensitive composition solution.

Examples of the solvent used herein include diisopropyl ether, mineral spirits, n-pentane, pentyl ether, ethyl octoate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, and hard Butyl fatty acid, n-octane, Varsol # 2, Apco # 18 solvent, diisobutylene, pentyl acetate, butyl acetate, Apco thinner, butyl ether, diisobutyl ketone, methyl cyclohexene, methyl nonyl Ketone, propyl ether, dodecane, Socal solvents No. 1 and No. 2, pentyl formate, dihexyl ether, diisoacetone, Solvesso # 150, acetic acid (n-, second, third) butyl ester, hexane Ene, Shell TS28 solvent, chlorobutane, ethylpentyl ketone, ethyl benzoate, chloropentane, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethylpentanone, methylbutyl ketone, Methylhexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl celex acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, pentyl acetate , Pentyl formate, bicyclohexane, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylpentyl ketone, methyl isopropyl ketone, propyl propionate, Propylene glycol tert-butyl ether Methyl ethyl ketone, methyl celex, ethyl celex, ethyl celex acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3 -Ethoxypropionic acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methyl Propyl oxypropionate, 3-methoxy propyl butyl ester, diethylene glycol dimethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol third butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate, and the like. These solvents may be used alone or in combination of two or more.

In the coloring photosensitive composition of the present invention, the content of the solvent is not particularly limited, and from the viewpoint of ease of coating or film thickness control at the time of coating film formation, it is usually preferably 90% by weight or less, and is usually preferable. It is 60% by weight or more, and particularly preferably 70% by weight or more. That is, it is preferable to prepare it in the coloring photosensitive composition of this invention so that total solid content concentration may become 10 weight% or more normally 40 weight% or less, especially 30 weight% or less.

[2-6] (f) Dispersant

In order to improve the dispersibility of the colorant and improve the dispersion stability, the photosensitive resin composition of the present invention uses a dispersant.

In the present invention, an acrylic block copolymer containing a nitrogen atom is used as a dispersant. It is presumed that such acrylic block copolymers containing nitrogen atoms have an affinity for the surface of the colorant due to the nitrogen atoms contained therein, and the non-nitrogen atoms increase the affinity for the medium, thereby contributing to the improvement of dispersion as a whole. stability.

The performance of a dispersant is its adsorption behavior on a solid surface. Although the detailed mechanism of the reason why the block copolymer has excellent adsorption behavior is not clear, it is estimated as follows.

That is, in the case of a normal random copolymer, the probability that the monomers constituting the copolymer are three-dimensionally and / or electrically stably arranged in the copolymer during copolymerization is high. Since the part (molecule) in which the monomer is stably arranged is three-dimensional and / or electrically stable, there is a case where it becomes an obstacle when adsorbed on the colorant. In contrast, a resin in which the molecular sequence is controlled like a block copolymer can arrange a portion that prevents the dispersant from being adsorbed away from the adsorption portion of the pigment and the dispersant. That is, the part that is most suitable for adsorption can be arranged in the adsorption part of the colorant and the dispersant, and the part suitable for it can be arranged in the part that requires solvent affinity. It is speculated that, especially with regard to the dispersion of colorants containing smaller coloring agents, the molecular configuration affects good dispersibility.

In terms of being able to disperse the coloring agent used in the present invention extremely efficiently, an acrylic block copolymer containing a nitrogen atom is preferred. The reason is not clear, but it is presumed that by controlling the molecular sequence, the dispersant has fewer structures that become obstacles when adsorbed to the colorant. The acrylic block copolymer is preferably at least one of an AB block copolymer and a BAB block copolymer. The AB block copolymer and the BAB block copolymer include a side chain having a fourth-order ammonium salt group and The A block of at least one of the amine groups and the B block having no quaternary ammonium salt group and amine group.

When the A block group having a quaternary ammonium salt of the case, the quaternary ammonium salt group is preferably in ^{-N + R 21 R 22 R 23} ‧M - ( wherein, R ^21, R ²² and R ²³ each independently represent A hydrogen atom or a substituted cyclic or chain hydrocarbon group; or two or more of R ²¹ , R ^22, and R ²³ may be bonded to each other to form a cyclic structure; M ^- represents a counter anion). The quaternary ammonium salt group may be directly bonded to the main chain, or may be bonded to the main chain through a divalent linking group.

In -N ⁺ R ²¹ R ²² R ²³ , as a cyclic structure formed by bonding two or more of R ²¹ , R ²² and R ²³ to each other, for example, a nitrogen-containing heterocyclic monocyclic ring having 5 to 7 members may be mentioned Ring or two of them. The nitrogen-containing heterocyclic ring is preferably one having no aromaticity, and more preferably a saturated ring. Specific examples include the following. These cyclic structures may further have a substituent.

(In the above formula, R represents any one of R ²¹ to R ^23. )

As in the -N ⁺ R ^{21 R 22 R 23 R 21 ~} R 23, more preferably may have a substituent group of carbon number 1 ~ 3 alkyl group, the group may have a substituent of a phenyl or benzyl substituent may have a group of base.

In addition, as the A block having a quaternary ammonium salt group, it is particularly preferred to have a partial structure represented by the following general formula (VI).

(In the above formula (VI), R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a cyclic or chain hydrocarbon group which may be substituted; or two or more of R ²¹ , R ^22, and R ²³ may be Bonded to each other to form a cyclic structure; R ²⁴ represents a hydrogen atom or a methyl group; X represents a divalent linking group, and M ^- represents a counter anion.)

In the general formula (VI), the hydrocarbon groups of R ²¹ , R ²² , and R ²³ are each independently a substituent having an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 20 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, benzyl, and phenyl. Among them, methyl, ethyl, propyl and benzyl are preferred.

Examples of the divalent linking group X in the general formula (VI) include an alkylene group having 1 to 10 carbon atoms, an arylene group, -CONH-R ^25- , -COO-R ^26- (wherein R ²⁵ And R ²⁶ represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (-R ²⁷ -OR ^28- : R ²⁷ and R ²⁸ are each independently an alkylene group), etc., -COO-R ²⁶ -is preferable.

Examples of the counter anion M ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ and the like.

One A block may contain two or more types of partial structures containing a specific quaternary ammonium salt group as described above. In this case, two or more types of partial structures containing a fourth-order ammonium salt group may be contained in the A block by random copolymerization or block copolymerization. In addition, a partial structure that does not include the fourth-order ammonium salt group may be contained in the A block. Examples of the partial structure include the following partial structures derived from (meth) acrylate-based monomers.

The content of the fourth-stage ammonium salt-free portion structure in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, and most preferably, the A-block is not included in the A-block. Partial structure of ammonium salt.

In addition, the A block of the acrylic block copolymer may have an unreacted tertiary amine group that has not been quaternized.

When the A block has an amine group, the amine group may be any of 1 to 3 grades. The content ratio of the monomer having 1 to 3 amine groups in the monomer composition constituting the acrylic block copolymer is preferably 20 mol% or more, and more preferably 50 mol% or more.

This amine group may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group.

In addition, as the first to third amine groups, -NR ⁴¹ R ⁴² (wherein R ⁴¹ and R ⁴² each independently represent a cyclic or chain alkyl group which may have a substituent, and An aryl group or an aralkyl group which may have a substituent is represented, and a structure (repeating unit) containing a partial structure (repeating unit) preferably is, for example, a structure represented by the following general formula.

(Wherein R ⁴¹ and R ⁴² have the same meanings as R ⁴¹ and R ⁴² described above, R ⁴³ represents an alkylene group having 1 or more carbon atoms, and R ⁴⁴ represents a hydrogen atom or a methyl group.)

Among them, R ⁴¹ and R ^{42 are} preferably methyl, R ^{43 is} preferably methylene and ethylene, and R ^{44 is} preferably a hydrogen atom or a methyl group. As such a partial structure, a structure derived from dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate represented by the following general formula can be particularly preferably used.

(In the above formula, R ⁴⁴ has the same meaning as above.)

Furthermore, one A block may contain two or more of the above-mentioned amine group-containing partial structures. In this case, the two or more types of amine group-containing partial structures may be contained in the A block in any one of random copolymerization and block copolymerization. In addition, a partial structure that does not contain an amine group may be partially contained in the A block. Examples of such a partial structure include a partial structure derived from a (meth) acrylate-based monomer. The content of the amine group-free portion structure in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, and most preferably the A block does not include the amine group-free portion structure. .

The A block may have either a quaternary ammonium salt group or an amine group, or both. Grade 4 ammonium salts have lower solubility for solvents with lower polarity, and amine groups have higher solubility for solvents with lower polarity. Therefore, when a relatively low-polarity solvent is used in a large amount of the resist, from the viewpoint of improving the solubility of the dispersant in the resist solvent, it is preferred that the A block has a level 4 ammonium salt group and an amine group. Or it may have an amine group without having a quaternary ammonium salt group, and more preferably have an amine group without having a quaternary ammonium salt group.

On the other hand, the B block constituting the acrylic block copolymer is not particularly limited as long as it does not have the above-mentioned quaternary ammonium salt group and amine group, and contains a monomer copolymerizable with the monomer constituting the A block. limit. The B block is a solvent-free site having no nitrogen atom-containing functional group that becomes a pigment-adsorbing group, and has an affinity for the solvent. Therefore, it has the function of stabilizing the pigment adsorbed in the dispersant in the solvent.

Examples of the B block include a copolymer structure obtained by copolymerizing a comonomer as described below. The comonomer is: a styrene-based monomer such as styrene or α-methylstyrene; (methyl ) Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, epoxypropyl ethyl acrylate, -N (meth) acrylic acid , (Meth) acrylic acid ester monomers such as N-dimethylaminoethyl ester; (meth) acrylic acid monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N, N (Meth) acrylamide-based monomers such as hydroxymethacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethylacrylamide; vinyl acetate; propylene Nitrile; Allyl Glycidyl Ether, Butyl Glycidyl Ether; N-Methacryl Porphyrin, etc.

As the B block, a structure containing a (meth) acrylic acid ester-based monomer represented by the following formula (VIII) is particularly preferred.

(In the above formula (VIII), R ⁴¹ represents a hydrogen atom or a methyl group; R ⁴² represents a cyclic or chain alkyl group which may have a substituent, an allyl group which may have a substituent, or an aromatic group which may have a substituent alkyl.)

One B block may contain two or more types of the above-mentioned (meth) acrylic acid-based monomer-containing partial structures. Of course, this B block may further contain a structure other than these. When two or more types of monomer-derived partial structures are present in the B block that does not contain a level 4 ammonium salt group, each of the partial structures may be randomly copolymerized or block copolymerized. It is contained in this B block.

When the B block contains a part structure other than the above-mentioned (meth) acrylate-based monomer structure, the content of the structure other than the (meth) acrylate monomer in the B block It is preferably 0 to 99% by weight, and more preferably 0 to 85% by weight.

The acrylic dispersant used in the present invention is an AB block or BAB block copolymer type polymer compound containing such A block and B block. Such a block copolymer is prepared, for example, by a living polymerization method. .

The living polymerization method includes anionic living polymerization method, cationic living polymerization method, and radical living polymerization method. For example, the method described in Japanese Patent Laid-Open No. 2007-270147 can be cited.

In addition, the amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content. The preferred range is because the A block has a level 4 ammonium salt group and the A block does not. The situation for the level 4 ammonium salt varies. The amine value is a value expressed in mg of KOH corresponding to the molar equivalent of the acid required to neutralize the amine group in 1 g of the copolymer.

That is, in the case of the AB block copolymer and the BAB block copolymer of the present invention, when the A block has a level 4 ammonium salt group, the amount of the level 4 ammonium salt group in 1 g of the copolymer is usually preferably 0.1. ~ 10mmol, if it is outside this range, there may be a case where it is impossible to have both good heat resistance and dispersibility.

Furthermore, in such a block copolymer, the amine group generated in the manufacturing process may be contained, and its amine value is usually about 1 to 100 mgKOH / g, and preferably 1 to 80 mgKOH / g. More preferably, it is 1 to 50 mgKOH / g.

In the case where the A block does not contain a level 4 ammonium salt group, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably 50 to 200 mgKOH / g, more preferably 80 mgKOH / g or more 150 mgKOH / g or less, and more preferably 90 to 150 mgKOH / g.

The acid value of such acrylic block copolymers also depends on the presence and type of the acidic group that is the source of the acid value. Generally, a lower value is preferred, usually 100 mgKOH / g or less, and preferably 50 mgKOH / g or less. , More preferably 40 mgKOH / g or less.

The molecular weight of the acrylic block copolymer is usually in the range of 1,000 or more and 100,000 or less as a weight average molecular weight (Mw) in terms of polyethylene measured by GPC. If the molecular weight of the acrylic block copolymer is too small, the dispersion stability tends to decrease, and if it is too large, the developability and resolution tend to decrease.

In the present invention, a commercially available acrylic block copolymer having the same structure as the above may be used.

In the present invention, the content of the acrylic block copolymer containing a nitrogen atom is usually 5% by weight or more and 90% by weight or less with respect to the pigment, preferably 5% by weight or more and 60% by weight or less, and further preferably 5 At least 40% by weight. If the content of the acrylic block copolymer containing a nitrogen atom is too small, sufficient dispersibility may not be obtained. If it is too large, the proportion of other components may be relatively reduced, the voltage holding ratio may be reduced, and the coloring interval may not be formed. The shape and step of the piece.

In the present invention, a dispersant other than the acrylic block copolymer containing a nitrogen atom may be used in combination. The dispersant used in combination is preferably a polymer dispersant, and a copolymer having a completely different structure from the coloring agent is preferable.

Examples of the dispersant used in combination include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant containing a monomer having an amine group and a macromonomer, and a polyoxyethylene alkyl ether-based dispersant. , Polyoxyethylene diester-based dispersant, polyether phosphoric acid-based dispersant, polyester phosphoric acid-based dispersant, sorbitan aliphatic ester-based dispersant, aliphatic modified polyester-based dispersant, and the like.

In order to improve the dispersion stability of the colorant, it is preferable to use a dispersion aid in combination with the coloring photosensitive composition of the present invention. The dispersing assistant herein refers to a pigment derivative or the like for improving the dispersibility of a colorant.

Examples of the pigment derivative include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, and Series, anthraquinone series, indanthrene series, stilbene series, purple ring ketone series, diketopyrrolopyrrole series, two Derivatives, such as quinolone, are preferred. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamido group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylamino group, a hydroxyl group, a carboxyl group, and a fluorenyl group. Those bonded to the pigment skeleton directly or via an alkyl group, an aryl group, or a heterocyclic group are preferably a sulfonic acid group. In addition, these substituents may substitute several for one pigment skeleton.

Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, and diketopyrrolopyrrole Sulfonic acid derivatives, di Sulfonic acid derivatives.

These pigment derivatives can be used individually by 1 type or in combination of 2 or more types.

When a pigment derivative is used, the amount used is generally 0.1 to 30% by weight relative to the pigment, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight. .

[2-7] other ingredients

The light-shielding sexy light resin composition of the present invention may further contain a polymerization accelerator, a sensitizing dye, a surfactant, a photoacid generator, a cross-linking agent, an adhesion improving agent, a plasticizer, Storage stabilizers, surface protection agents, organic carboxylic acids, organic carboxylic anhydrides, development improvers, thermal polymerization inhibitors, etc.

[2-7-1] Photoacid generator

The photoacid generator refers to a compound capable of generating an acid by ultraviolet rays, and a cross-linking reaction occurs due to the presence of a crosslinking agent such as a melamine compound due to the action of an acid generated during exposure. Among the photoacid generators, those having a high solubility in a solvent, particularly those having a large solubility in a solvent used for coloring a photosensitive composition, are preferred. Examples include diphenylphosphonium, xylylphosphonium, and benzene. P-anisylfluorene, bis (m-nitrophenyl) fluorene, bis (p-thirdbutylphenyl) fluorene, bis (p-chlorophenyl) fluorene, bis (n-dodecyl) fluorene, p-isobutyl Diarylfluorene such as p-phenylphenyl p-tolylfluorene and p-isopropylphenyl p-tolylfluorene; or chlorides and bromides of triarylfluorene such as triphenylfluorene; or fluoroborate, hexafluorophosphate, Hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc .; or fluorene organoborium complexes such as n-butyltriphenylborate diphenylbenzyl methyl hydrazone; or 2-methyl-4,6-bis (trichloromethyl) tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) tri Wait three Compounds and the like are not limited thereto.

[2-7-2] Crosslinking agent

You may further add a crosslinking agent to the coloring photosensitive composition of this invention, For example, a melamine or a guanamine type compound can be used. Examples of such a crosslinking agent include melamine or guanamine-based compounds represented by the following general formula (XI).

[Chemical 14]

(In the formula, R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or an aryl group. When R ⁶¹ is a -NR ⁶⁶ R ⁶⁷ group, one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ Represents a -CH ₂ OR ⁶⁸ group, and when R ⁶¹ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents a -CH ₂ OR ⁶⁸ group, R ⁶² , R ⁶³ , R ⁶⁴ , R ⁽⁶⁵ , R ^66, and R ⁶⁷ independently represent hydrogen or -CH ₂ OR ⁶⁸ , and R ⁶⁸ represents hydrogen or alkyl.)

Here, the aryl group is typically a phenyl group, a 1-naphthyl group, or a 2-naphthyl group, and substituents such as an alkyl group, an alkoxy group, and a halogen group may be bonded to the phenyl or naphthyl group. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is usually a methyl group or an ethyl group, especially a methyl group.

The melamine-based compound corresponding to the general formula (XI), that is, the compound of the following general formula (XI-1) includes hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, and hexamethoxymethylmelamine , Pentamethoxymethyl melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, etc.

(In the formula, when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ represents -CH ₂ OR ^{68 Group} , the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently represent a hydrogen or -CH ₂ OR ⁶⁸ group, where R ⁶⁸ represents hydrogen or an alkyl group.)

In addition, guanamine-based compounds corresponding to the general formula (XI), that is, compounds in which R ⁶¹ in the general formula (XI) is an aryl group, include tetramethylolbenzoguanamine and tetramethoxymethylbenzoguanidine. Amine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, and the like.

Furthermore, a crosslinking agent having a methylol group or a methylol alkyl ether group may be used. Examples are given below.

2,6-bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) Perhydro-1,3,5-tri -2-one (commonly known as N-ethyldimethyloltriol Ketone) or its dimethyl ether body, dimethyloltrimethylene urea or its dimethyl ether body, 3,5-bis (hydroxymethyl) perhydro-1,3,5- two 4-ketone (commonly known as dimethyloluron) or its dimethyl ether body, tetramethylol glyoxal dialkyl urea or its tetramethyl ether body.

In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more type. The amount when the crosslinking agent is used is preferably 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight, relative to the total solids content of the light-shielding photosensitive resin composition.

[2-7-3] Adhesion improving agent

In order to make the thinner threads or dots sufficiently close to each other, an adhesion improving agent may be contained in the light-shielding and sexy light-sensitive resin composition of the present invention.

The adhesion improving agent is preferably a compound containing a nitrogen atom, a compound containing a phosphate group, a silane coupling agent, and the like, and a compound containing a nitrogen atom is, for example, a diamine (Japanese Patent Application Laid-Open No. 11-184080) (Tightening enhancer, etc.) or azoles. Among them, azoles are preferred, and imidazoles (adhesion improvers described in Japanese Patent Laid-Open No. 9-236923) are particularly preferred, benzimidazoles, and benzotriazoles (Japanese Patent Laid-Open No. 2000-171968). As described in the adhesion improving agent, etc.), the most preferred are imidazoles and benzimidazoles. Among these, 2-hydroxybenzimidazole, 2-hydroxyethyl benzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole, 2-mercaptoimidazole, 2-aminoimidazole, particularly preferably 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole. As the type of the silane coupling agent, each of epoxy-based, methacrylic-based, and amine-based can be used, and an epoxy-based silane coupling agent is particularly preferred.

These can be used individually by 1 type or in combination of 2 or more types.

When blending these adhesion improving agents, the blending ratio varies depending on the type of adhesion improving agent used, and it is preferably set to 0.01 to 5% by weight relative to the total solid content of the coloring photosensitive composition. It is particularly preferably set to 0.05 to 3% by weight. If it is less than this, the effect which fully improves adhesiveness may not be acquired, and when it is too much, developability may fall.

[2-7-4] sensitizing pigment

Examples of the sensitizing dye include those described in Japanese Patent Laid-Open No. 4-221958 and Japanese Patent Laid-Open No. 4-219756. Pigments, coumarin pigments having heterocyclic rings described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, Japanese Patent Laid-Open No. 3-239703, and Japanese Patent Laid-Open No. 5-239703. In addition to the 3-ketocoumarin compounds described in Japanese Patent Publication No. 289335 and the pyrrole methylene pigment described in Japanese Patent Application Laid-Open No. 6-19240, Japanese Patent Application Laid-Open No. 47-2528 can be cited. Japanese Patent Laid-Open No. 54-155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58 -15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent A pigment having a dialkylaminobenzene skeleton described in Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, and Japanese Patent Laid-Open No. 4-288818.

These can be used individually by 1 type or in combination of 2 or more types.

When the sensitizing dye is blended, the content ratio of the sensitizing dye in the total solid content in the colored photosensitive composition is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight. If it is less than this, a sensitization effect may not be exhibited, and if it is too much, developability may fall.

[2-7-5] Surfactants

As the surfactant, one or more kinds of various surfactants, such as anionic, cationic, nonionic, and amphoteric surfactants, can be used, and the possibility of adversely affecting each characteristic is low. Preferably, a non-ionic surfactant is used. Further, a fluorine-based or silicon-based surfactant is more effective in terms of coatability.

The blending ratio of the surfactant is generally in the range of 0.001 to 10% by weight, preferably in the range of 0.005 to 1% by weight, and more preferably 0.01 to 0.5% by weight relative to the total solid content in the colored photosensitive composition. The range of% is preferably in the range of 0.03 to 0.3% by weight. If the amount of the surfactant added is less than the above range, there may be cases where the smoothness and uniformity of the coating film cannot be expressed. If it is more than the above range, there may be cases where the smoothness and uniformity of the coating film cannot be expressed. In addition, other characteristics may deteriorate.

[2-7-6] organic carboxylic acid, organic carboxylic anhydride

The coloring photosensitive composition of the present invention may contain at least one of an organic carboxylic acid and an organic carboxylic anhydride in order to improve developability or improve plate stain.

Examples of the organic carboxylic acid include at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid.

Specific examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, hexanoic acid, diethylacetic acid, heptanoic acid, caprylic acid, glycolic acid, acrylic acid, and methacrylic acid. Monocarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecanedioic acid, methylmalonic acid , Ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, itaconic acid, methylmaleic acid , Maleic acid, fumaric acid and other dicarboxylic acids, 1, 2, 3-malonic acid, aconitic acid, Tricarboxylic acids and the like. Specific examples of the aromatic carboxylic acid include benzoic acid, toluic acid, cuminic acid, 2,3-dimethylbenzoic acid, 3,5-dimethylbenzoic acid, phthalic acid, and o-phthalic acid. Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, 1,2,3,5-benzenetetracarboxylic acid, pyromellitic acid, phenylacetic acid, hydrogen attoric acid, hydrogen Cinamic acid, picric acid, phenylsuccinic acid, atoric acid, cinnamic acid, methyl cinnamic acid, benzyl cinnamic acid, cinnamic acid, coumaric acid, umbellic acid, etc. Carboxylic acid, carboxylic acid having carboxyl group bonded to the phenyl group via a carbon bond, and the like.

Among the above-mentioned organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferred, and among them, malonic acid, glutaric acid, and glycolic acid are more preferred, and malonic acid is particularly preferred.

The molecular weight of the organic carboxylic acid is usually 1,000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving plate stain may be insufficient. If it is too small, the amount of addition may be reduced due to sublimation, volatilization, etc., or the step may be polluted.

Examples of the organic carboxylic acid anhydride include at least one of an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride. Examples of the aliphatic carboxylic acid anhydride include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, and tetrahydroortho. Phthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, methyl maleic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride 5-down Aliphatic carboxylic anhydrides such as ene-2,3-dicarboxylic anhydride. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalenedicarboxylic anhydride.

Among the organic carboxylic anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and methyl maleic anhydride are preferred, and maleic anhydride is further preferred.

The molecular weight of the organic carboxylic anhydride is usually 800 or less, preferably 600 or less, more preferably 500 or less, and usually 50 or more. If the molecular weight of the organic carboxylic anhydride is too large, there may be cases where the effect of improving plate staining is insufficient. If it is too small, the amount of addition may be reduced due to sublimation, volatilization, etc., or the step may be contaminated.

These organic carboxylic acids and organic carboxylic anhydrides may be used singly or in combination of two or more kinds.

The addition amounts of these organic carboxylic acids and organic carboxylic anhydrides are respectively in the total solid content of the light-shielding and photosensitive resin composition of the present invention, usually 0.01% to 5% by weight, preferably 0.03% to 3% by weight. . If the added amount is too small, a sufficient addition effect may not be obtained, and if it is too large, surface smoothness or sensitivity may be deteriorated, and an undissolved release sheet may be generated.

[2-7-7] Thermal polymerization inhibitor

As the thermal polymerization inhibitor, for example, one of hydroquinone, p-methoxyphenol, catechol, catechol, 2,6-tert-butyl-p-cresol, and β-naphthol can be used. One or two or more.

The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight relative to the total solid content in the light-shielding photosensitive resin composition. If it is more than this, the light-shielding and photosensitive resin composition may be reduced The sensitivity of the situation.

[2-7-8] Plasticizer

As the plasticizer, for example, dioctyl phthalate, di (dodecyl) phthalate, triethylene glycol dicaprylate, dimethyl ethylene glycol phthalate, One or two or more of tricresol phosphate, dioctyl adipate, dibutyl sebacate, triacetin, and glycerol.

The blending ratio of these plasticizers is preferably in the range of 5% by weight or less relative to the total solid content in the light-shielding and sexy resin composition. If more than this, the hardening point of the resin black matrix is reduced.

[3] Manufacturing method of colored photosensitive composition

Next, the manufacturing method of the coloring photosensitive composition of this invention is demonstrated.

Hereinafter, a coloring photosensitive composition using a pigment as a colorant will be described.

First, a pigment dispersion is produced using (a) a pigment and (f) a dispersant and necessary components. Then, the pigment dispersion liquid obtained above, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent are mixed to produce a colored photosensitive composition. If necessary, the other ingredients mentioned above can also be mixed.

[3-1] (a) Manufacturing method of pigment dispersion

As a method for producing the pigment dispersion liquid of the present invention, various methods can be adopted. One example is shown below.

First, a specific amount of a pigment, a solvent, and a dispersant / dispersion aid are weighed separately, and the pigment is dispersed in a dispersion treatment step to prepare a liquid pigment dispersion. As a pigment, a solvent, and a dispersing agent / dispersion adjuvant, what is described as a component of the said coloring photosensitive composition can be used.

In this dispersion treatment step, a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like can be used. When using a sand mill for dispersion treatment, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several millimeters.

Since the pigment is micronized by performing the dispersion treatment, the plate-making properties such as coating characteristics and linearity of the coloring photosensitive composition using the pigment dispersion liquid are improved.

When dispersing a pigment, the said alkali-soluble resin etc. can be used together suitably.

The temperature during the dispersion treatment is usually set in a range of 0 ° C to 100 ° C, and preferably in a range of room temperature to 80 ° C. In addition, since the dispersion time varies depending on the composition of the pigment dispersion liquid (pigment, solvent, dispersant / dispersion aid, etc.) and the size of the device of the sand mill, etc., the exact time must be appropriately adjusted.

The content of the (a) pigment in the pigment dispersion liquid is usually 5% by weight or more and 50% by weight or less, preferably 10% by weight or more and 40% by weight or less.

The content of the (f) dispersant in the pigment dispersion liquid is usually 5 wt% or more and 90 wt% or less, preferably 5 wt% or more and 60 wt% or less, and more preferably 5 wt% or more and 40% with respect to the pigment. Below weight.

The content of the dispersion aid in the pigment dispersion liquid is generally 0.1 to 30% by weight, preferably 0.1 to 20% by weight or less, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight relative to the pigment.

The content of the alkali-soluble resin (b) in the pigment dispersion liquid is usually 0% by weight or more and 100% by weight or less with respect to the pigment, preferably 5% by weight or more and 80% by weight or less, and further preferably 5% by weight or more and 60% by weight or less.

[3-2] Manufacturing method of colored photosensitive composition

Next, the pigment dispersion liquid (ink) obtained by the above-mentioned dispersion treatment and the above-mentioned other components required for coloring the photosensitive composition component are added and mixed to prepare a uniform colored photosensitive composition solution. In this manufacturing step, since a lot of fine impurities are mixed in the solution, it is preferable to filter the colored photosensitive composition solution with a filter or the like.

In addition, the coloring photosensitive composition using other than a pigment (for example, a dye) as a colorant can be manufactured by a well-known method.

[4] Method for forming colored spacers

The colored photosensitive composition of this embodiment can be used in the same manner as the known colored photosensitive composition for color filters, and the case where it is used as a colored spacer will be described below.

Generally, the colored photosensitive composition solution is supplied in a film or pattern form to a substrate to be provided with a colored spacer by a method such as coating, and the solvent is dried. Then, a pattern is formed by a photolithography method in which exposure-development is performed. Thereafter, if necessary, additional exposure or thermosetting treatment is performed to form a colored spacer on the substrate.

[4-1] Supply method to substrate

The colored photosensitive composition of this embodiment is usually supplied to a substrate in a state of being dissolved or dispersed in a solvent. As a supply method thereof, a conventionally known method such as a spin coating method, a bar coating method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like can be used. Among them, if the extrusion coating method is used, the amount of coating liquid used can be greatly reduced, and there is no effect of fog and the like attached when the spin coating method is used, and it is preferable to comprehensively suppress the generation of impurities and the like. .

The coating amount varies depending on the application. For example, in the case of a colored spacer, the dry film thickness is usually in a range of 0.5 μm to 10 μm, preferably in a range of 1 μm to 9 μm, and particularly preferably in a range of 1 μm to 7 μm. In addition, it is important that the thickness of the dried film or the height of the colored spacer to be finally formed is uniform over the entire area of the substrate. When the deviation is large, uneven defects may occur in the liquid crystal panel. It can also be supplied in a pattern form by an inkjet method or a printing method.

Further, a known substrate such as a glass substrate can be used as the substrate. The surface of the substrate is preferably flat.

[4-2] Drying method

The drying method after the colored photosensitive composition solution is supplied onto the substrate is preferably a drying method using a hot plate, an IR (infrared) oven, or a convection oven. Further, a reduced-pressure drying method in which drying is performed in a decompression chamber without increasing the temperature may be combined.

The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. Drying time can be selected within the range of 15 seconds to 5 minutes at a temperature of 40 ° C to 130 ° C, and preferably at a temperature of 50 ° C to 110 ° C, depending on the type of solvent composition and the performance of the dryer used. Choose from 30 seconds to 3 minutes.

[4-3] Exposure method

The exposure is performed by superposing a negative mask pattern on the coating film of the colored photosensitive composition, and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In the case of using an exposure mask for exposure, a method of bringing the exposure mask close to the coating film of the colored photosensitive composition, or arranging the exposure mask at a position away from the coating film of the colored photosensitive composition, A method of projecting light that is exposed through the exposure mask. In addition, a scanning exposure method using laser light without using a mask pattern may be used. At this time, in order to prevent a decrease in the sensitivity of the photopolymerizable layer caused by oxygen, it may be performed in a deoxidizing environment, or exposed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

The light source used for the above exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, and fluorescent lamps, or argon ion lightning Laser, YAG (Yttrium Aluminum Garnet) laser, excimer laser, nitrogen laser, helium-cadmium laser, blue-violet semiconductor laser, near-infrared semiconductor laser and other laser light sources. When using light of a specific wavelength, an optical filter can also be used.

The optical filter may be, for example, a type in which the light transmittance at the exposure wavelength can be controlled by a thin film. As a material in this case, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride) Etc.), MoSi, Si, W, Al, etc.

In addition, in the method for forming colored spacers of different heights at one time by a photolithography method, the following methods may be used: a light-shielding layer having a light-shielding layer and an opening through which light is transmitted, and a part thereof As an exposure mask, an exposure mask having an average transmittance smaller than the average transmittance of other openings is used as the exposure mask. That is, a light-shielding layer (light transmittance 0%) and several openings are used as the exposure mask. A method of exposing a mask having an opening portion (middle penetration opening portion) having a small average light transmittance (usually a light transmittance of 100%; hereinafter referred to as a fully penetrating opening portion).

As a method of forming the intermediate penetrating opening portion, a method using a mask may be adopted in which the above-mentioned optical filter is arbitrarily arranged on the opening portion (light transmitting portion) of the mask pattern, that is, appropriately arranged with The opening portion (middle penetration opening portion) of the optical filter and the opening portion (complete penetration opening portion) where no optical filter is provided. Thereby, a pattern having a different photopolymerization rate corresponding to the light transmittance of the opening portion can be formed by one exposure step, for example, patterns having different heights can be formed at the same time by one exposure step.

Also, as another method for forming the intermediate penetrating opening portion, it is also possible to arrange the light-shielding portion and the fully penetrating portion described in Japanese Patent Application Laid-Open No. 2003-344860 into a small matrix pattern shape or a narrow slit. The slit pattern is formed to form an exposure mask having an average light transmittance adjusted (the light transmittance is smaller than that of the full penetration opening) with an intermediate penetration opening.

As the exposure amount of the present embodiment, generally 1mJ / cm ² or more, preferably from 5mJ / cm ² or more, more preferably 10mJ / cm ² or more, and usually ² or less 300mJ / cm, preferably 200mJ / cm ² or less, more preferably 150 mJ / cm ² or less.

In the case of approaching the exposure method, the distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, and more preferably 300 μm or less.

[4-4] Development method

After the exposure is performed, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye, or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphoric acid. Inorganic basic compounds such as potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, or mono / di / triethanolamine, mono / di / trimethylamine, mono / di / triethyl Amine, mono / diisopropylamine, n-butylamine, mono / di / triisopropanolamine, ethyleneimine, ethylenediimine, tetramethyl ammonium hydroxide (TMAH), bile Organic basic compounds such as alkali. These basic compounds may be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceryl alkyl groups. Nonionic surfactants such as esters; anionic properties such as alkylbenzenesulfonates, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, sulfosuccinates, etc. Surfactants; Ampholytic surfactants such as alkyl betaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cyrus, butyl cyrus, phenyl cyrus, propylene glycol, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

There is no particular limitation on the method of the development treatment, and it is usually carried out at a development temperature of 10 ° C to 50 ° C, preferably 15 ° C to 45 ° C, by immersion development, jet development, brush development, ultrasonic development, or the like.

[4-5] Additional exposure and thermal hardening

If necessary, additional exposure may be performed on the substrate after development by the same method as the above-mentioned exposure method, and a thermosetting treatment may also be performed. Regarding the heat curing treatment conditions at this time, the temperature can be selected in the range of 100 ° C to 280 ° C, preferably 150 ° C to 250 ° C, and the time can be selected in the range of 5 minutes to 60 minutes.

The colored photosensitive composition of this embodiment is preferably used for forming a black matrix, a surface coating layer, a barrier rib, a colored spacer, and the like in a color filter or the like in a liquid crystal display. In addition, it is possible to provide a coloring photosensitive composition suitable for a method for simultaneously forming a coloring spacer having particularly different heights by a photolithography method. In addition, according to this embodiment, a high-quality color filter, a liquid crystal display device, and the like can be provided.

[5] colored spacers

The colored spacer formed by the colored photosensitive composition of the present invention is preferably a substantially cylindrical spacer pattern.

The diameter of the cross section under the pattern of the colored spacer which completely penetrates the opening is usually more than 15 m and less than 45 m, preferably more than 18 m and less than 40 m. When it is lower than this range, there is a tendency that the compression characteristics are deteriorated. When it is higher than this range, the area on the substrate is increased, so it is not good in terms of panel structure.

The cross-sectional diameter under the colored spacer pattern of the intermediate penetration opening is usually more than 20 μm and less than 50 μm, and preferably more than 30 μm and less than 40 μm. If the range is lower than this range, the compression characteristics tend to be deteriorated. If the range is higher than this range, the area on the substrate is increased, which is not good in terms of panel structure.

Regarding the difference (△ H) between the height of the colored spacer pattern that completely penetrates the opening and the height of the colored spacer pattern that penetrates the opening, the height of the colored spacer pattern that completely penetrates the opening exceeds 2.8 μm and When it is less than 3.2 μm, it is usually 0.25 μm or more and 1.0 μm or less, preferably 0.35 μm or more and 0.80 μm or less, and more preferably 0.4 μm or more and 0.6 μm or less. When it falls below this range, the load resistance tends to deteriorate, and when it falls above this range, the compression limit tends to be exceeded.

[6] Color filters

The color filter of the present invention includes the coloring spacer of the present invention as described above, for example, a black matrix and red, green, and blue pixel coloring layers are laminated on a glass substrate as a transparent substrate, and a surface coating layer, and An alignment film is formed after the colored spacers are formed. The alignment film is preferably a resin film such as polyimide.

[7] Liquid crystal display device

The liquid crystal display device of the present invention includes the color filter having the color spacer of the present invention as described above, and for example, the color filter and the liquid crystal driving side substrate are bonded together to form a liquid crystal cell. It is manufactured by injecting liquid crystal into the formed liquid crystal cell.

Examples

Next, the present embodiment will be described more specifically by citing examples and comparative examples. The present embodiment is not limited to the following examples as long as it does not exceed the gist thereof.

The constituents of the colored photosensitive composition used in the following examples and comparative examples are as follows.

In the following, "part" means "part by weight".

    <Alkali soluble resin-1>    

"ADEP02" (MW = 3500 ~ 4500, acid value = about 110mg-KOH / g, equivalent to alkali-soluble resin (A-2)) manufactured by Shin Nakamura Chemical Industry Co., Ltd.

    <Alkali soluble resin-2>    

"ZCR-1664H" (MW = 5000 ~ 6000, acid value = about 60mg-KOH / g, equivalent to alkali-soluble resin (A-1)) manufactured by Nippon Kayaku Co., Ltd.

    <Alkali soluble resin-3>    

"SPCM-82" manufactured by Showa Polymer Co., Ltd. (MW = approximately 10,000, acid value = approximately 24mg-KOH / g, acrylate-based alkali-soluble resin)

    <Alkali soluble resin-4>    

In a 500 mL four-necked flask, 61.2 g of styrene-acrylic resin and Joncryl 680 (BASF JAPAN Co., Ltd.) were uniformly dissolved in 138.6 g of propylene glycol monomethyl ether acetate at 80 ° C. 0.24 g of ammonium tetrachloride and 0.09 g of p-methoxyphenol were added and dissolved therein, and 71.4 g of propylene glycol monomethyl ether acetate and 3,4-epoxycyclohexyl methyl acrylate (Cyclomer A400) were added dropwise over 40 minutes. , Daicel Chemical Co., Ltd.) 19.9 g of the mixed liquid. The reaction solution was stirred for 32 hours while maintaining the temperature at 80 ° C to obtain a resin having a weight average molecular weight of 6700 and an acid value of 106 mgKOH / g.

    <Alkali soluble resin-5>    

"SPCM-121B" manufactured by Showa Polymer Co., Ltd. (MW = approximately 8300, acid value = approximately 80mg-KOH / g, acrylate-based alkali-soluble resin)

    <Dispersant-1>    

"DisperBYK-2000" manufactured by BYK-Chemie (acrylic A-B block copolymer containing an A block with a 4th level ammonium salt group and a B block without a 4th ammonium salt group in the side chain)

    <Dispersant-2>    

"DisperBYK-LPN21116" manufactured by BYK-Chemie (including A-blocks with side-chain ammonium salt and amine groups in the side chain and acrylic AB blocks without B-blocks with quaternary ammonium salt and amine groups Fit

    <Dispersant-3>    

"DisperBYK-167" (urethane-based dispersant) manufactured by BYK-Chemie

    <Dispersion aid>    

"S12000" made by Lubrizol

    <Surfactant>    

Megafac F-475 manufactured by Dainippon Ink and Chemicals

    <Solvent-1>    

PGMEA (propylene glycol methyl ether acetate): propylene glycol methyl ether acetate

    <Solvent-2>    

MB (3-methoxybutanol): 3-methoxybutanol

    <Solvent-3>    

MBA (3-methoxybutyl acetate): 3-methoxybutyl acetate

    <Solvent-4>    

CHN (cyclohexanone): cyclohexanone

    <Photopolymerization initiator>    

A compound represented by the following formula.

    <Ethylene unsaturated compound>    

DPHA (dipentaerythritol hexaacrylate): Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

    <Preparation of Pigment Dispersion Liquids 1-4>    

The pigments, dispersants, dispersion aids, alkali-soluble resins, and propylene glycol monomethyl ether acetate (PGMEA) and methoxybutyl acetate (MBA) described in Table 1 are mixed in a weight ratio described in Table 1. . After mixing 80% of the volume of the dispersion container with zirconia beads, it was filled into the PICO MILL dispersion container and dispersed for the required residence time to prepare each pigment dispersion.

    [Examples 1 to 3, Comparative Examples 1 to 4]    

The pigment dispersion liquid prepared above and the components shown in Table 2 were blended at the ratios shown in Table 2 and stirred to prepare colored photosensitive composition coating liquids, respectively. Using the obtained colored photosensitive composition solution, a substantially cylindrical spacer pattern was formed by the following method, and the shape, step, adhesion to the substrate, and voltage holding ratio (VHR, Voltage Holding Ratio) were evaluated. The results are shown in Table 2.

    [Method for forming colored spacers of different heights at one time]    

The photosensitive composition was coated on the ITO film of a glass substrate having an ITO (Indium Tin Oxide) film formed on the surface using a spin coater. Then, it was heated and dried on a hot plate at 110 ° C. for 70 s to form a coating film. The dry film thickness was 3.5 μm.

The obtained coating film was subjected to an exposure treatment using an exposure mask having a full penetration opening portion having a circular pattern with a diameter of 15 μm and a middle penetration opening portion having a circular pattern with a diameter of 35 μm. A thin film of Cr oxide was used in the middle penetration opening to set the light transmittance at a wavelength of 365 nm to 12.1%, the light transmittance at 405 nm to 16.5%, and the light transmittance at 436 nm to 19.6%. In addition, the light transmittance before and after the three points is continuous, and there is no inflection point. The exposure pitch (distance between the mask and the coating surface) was 250 μm.

In addition, ultraviolet rays having an intensity of 32 mW / cm ² at 365 nm were used. The exposure amount was set to 50 mJ / cm ² . The ultraviolet irradiation was performed in the air. Then, using a 0.1% potassium hydroxide aqueous solution at 25 ° C., jet development was performed at 1.6 times the minimum development time, and then washed with pure water. Those who cannot dissolve even after 120 seconds are set as undeveloped.

With these operations, a pattern for removing unnecessary portions is obtained. The substrate on which the pattern was formed was heated in an oven at 230 ° C. for 20 minutes to harden the pattern to obtain a substantially cylindrical spacer pattern.

    [Shape measurement of colored spacer pattern]    

Regarding the above-mentioned substantially cylindrical colored spacer pattern, the longitudinal section was passed through the longitudinal section of the central axis of the colored spacer pattern, and the height of the colored spacer pattern and the cross-sectional diameters of the upper and lower bottom surfaces were measured. For measurement, a three-dimensional non-contact surface shape measuring system Micromap MM3500-M100 manufactured by Ryoka Systems Co., Ltd. was used.

1 (A) and 1 (B) are diagrams for explaining the shape of the above-mentioned substantially cylindrical spacer pattern. In FIG. 1 (A), the colored spacer pattern 1 is convexly formed on the glass substrate 2 and has a substantially circular shape in plan view. FIG. 1 (B) is an X-X cross-sectional view of the axis 3 passing through the colored spacer pattern 1 of FIG. 1 (A). In FIG. 1 (B), the colored spacer pattern 1 has a substantially rectangular outline. Let this outline be the cross section 4 of the colored spacer pattern 1, and let the intersection point of the pattern side surface part 41 of the cross section 4 and the glass substrate 2 be the intersection A, A '. The distance from the surface of the glass substrate 2 to the highest position point of the section 4 is the pattern height H, and the distance between the intersection point A and the intersection point A ′ is the lower section diameter L.

    [Evaluation of step]    

The difference (ΔH) between the height of the colored spacer pattern that completely penetrates the opening and the height of the colored spacer pattern that penetrates the middle of the opening is more than 0.35 μm and 0.8 μm or less. ○, and 0.25 μm or more and A value of 0.4 μm or less is Δ, and a value of less than 0.25 μm is X. The results are shown in Table 2.

    [Evaluation of tightness]    

In the manner described above, the sizes provided with the intermediate penetration openings are 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40, 45, 50 μm each has 24 photomasks in the middle penetrating openings, each forming 24 patterns with different sizes. The size (diameter) of the smallest intermediate penetrating opening where 24 patterns did not disappear was measured. A size of 15 μm or less is ○, and a size of more than 15 μm is X. The results are shown in Table 2.

    [Evaluation of Voltage Holding Rate (VHR)]    

The voltage retention ratio (VHR) was evaluated by the method described below, and the results are shown in Table 2.

    <Creating a liquid crystal cell>    

An electrode substrate A (made of EHC, glass ITO entire surface) with an ITO film formed on one side of 5 cm square was prepared, and an extraction of 2 mm width was formed at the center of one side of the same glass substrate of 2.5 cm square. Electrode substrate B (EHC, evaluation glass SZ-B111MIN (B)) of 1 cm square ITO film of the electrode.

Each colored photosensitive composition solution was coated on the electrode substrate A, and dried under vacuum for 1 minute, and then pre-baked on a hot plate at 110 ° C. for 70 s to obtain a coating film having a dry film thickness of 3.5 μm. Thereafter, the outer peripheral portion was shielded by 2 mm, and 3 kW high-pressure mercury was used to perform image exposure under an exposure condition of 50 mJ / cm ² . Then, using a 0.1% by weight potassium hydroxide aqueous solution at 25 ° C., spray development was performed at 25 ° C. with a water pressure of 0.15 MPa, development was stopped by pure water, and washing was performed by water jetting. The spray development time is adjusted from 10 to 120 seconds, and is set to about 1.6 times the time (break time) for dissolving and removing the photosensitive layer. Those who could not dissolve for 120 seconds were judged to be unable to develop.

The electrode substrate on which the image was formed as described above was baked at 230 ° C. for 20 minutes to obtain an electrode substrate (resist substrate) to which a resist was applied. Thereafter, a polyimide solution was coated on the resist substrate, pre-baked at 70 ° C for 2 minutes on a hot plate, and post-baked at 220 ° C for 24 minutes. The resist substrate obtained in the above manner was cut into a 2.5 cm square substrate to complete the electrode substrate A for evaluation.

On the other hand, the polyimide solution was also coated on the electrode substrate B, pre-baked at 70 ° C. for 2 minutes on a hot plate, and post-baked at 220 ° C. for 24 minutes to complete the electrode substrate B for evaluation.

Thereafter, an epoxy resin-based sealant containing silicon dioxide beads having a diameter of 5 μm was coated on the outer periphery of the electrode substrate B using a dispenser, and then the coated surface of the electrode substrate A for evaluation was pressure-bonded. On the front side (sealant side) of the electrode substrate B, an empty cell is completed. In a hot-air circulation furnace, it was heated at 180 ° C for 2 hours.

Liquid crystal (MLC-6608 manufactured by Merck Japan) was injected into the empty cell obtained in the above manner, and a peripheral portion was sealed with a UV (Ultraviolet) hardening sealant to complete a liquid crystal cell for measuring a voltage holding ratio.

    <Evaluation of Voltage Holding Rate (VHR)>    

After the above liquid crystal cell was annealed (heated in a hot air circulation furnace at 105 ° C. for 2.5 hours), a voltage of 5 V was applied to the electrode substrates A and B for evaluation at 0.6 Hz and a frame time of 1667 msec. "VHR-6254" manufactured by Corporation Co., Ltd. measures the voltage holding ratio.

From the results in Table 2, it can be seen that with the colored photosensitive composition of the present invention, it is possible to obtain the shape of the pattern of completely penetrating openings and intermediate penetrating openings, control of step difference, better adhesion, and the voltage of the liquid crystal. The colored spacer with excellent retention can be used for a method of forming colored spacers of different heights at one time.

The present invention has been described in detail and with reference to specific implementation aspects, but it should be understood by those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application filed on October 25, 2011 (Japanese Patent Application No. 2011-233900), the contents of which are incorporated herein by reference.

    (Industrial availability)    

The coloring photosensitive composition of the present invention can be preferably used when forming a coloring spacer or the like in a color filter of a liquid crystal display or the like, especially when forming coloring spacers of different heights at one time by a photolithography method. In this case, the shape formation, step difference, adhesion, and electrical reliability of the liquid crystal are excellent. The invention can provide a high-quality color filter or a liquid crystal display device.

Claims (14)

A colored photosensitive composition comprising (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant And used to form colored spacers of different heights at one time by photolithography; (a) the content ratio of the colorant is less than 30% by weight relative to the total solid content of the coloring photosensitive composition; it contains the following At least one of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) is (b) an alkali-soluble resin; an acrylic block copolymer containing a nitrogen atom is used as (f) a dispersant; (b) ) The weight ratio of the alkali-soluble resin to the (d) ethylenically unsaturated compound is less than 7; the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) is relative to that of the colored photosensitive composition. The proportion of the total solid content is 12% by weight or more; <Alkali-soluble resin (A-1)> By adding α, β-unsaturated monocarboxylic acid or ester portion to the epoxy resin, α, β-unsaturation Monocarboxylic acid ester, which is obtained by reacting with polybasic acid anhydride; <alkali soluble resin (A-2)> By adding α, β-unsaturated monocarboxylic acid to epoxy resin Or carboxyl ester moiety having α, [beta] unsaturated monocarboxylic acid esters, in turn obtained by reacting the resin with a polyol and polybasic acid anhydride. The colored photosensitive composition according to claim 1, wherein the ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20% by weight the above. For example, the colored photosensitive composition of claim 1, wherein the ratio of the total of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition is 20 to 60. weight%. The colored photosensitive composition according to any one of claims 1 to 3, wherein (a) the content ratio of the colorant is 25% by weight or more with respect to the total solid content in the colored photosensitive composition. The coloring photosensitive composition according to any one of claims 1 to 3, wherein (a) the colorant contains the following (1) red pigment, and the following (2) blue pigment and ( 3) At least one of the purple pigments; (1) a red pigment selected from CI Pigment Red 177 and 254; (2) a blue pigment belonging to CI Pigment Blue 15: 6; (3) a violet belonging to CI Pigment Violet 23 pigment. The colored photosensitive composition according to any one of claims 1 to 3, which contains C.I. Pigment Red 254 and C.I. Pigment Blue 15: 6 as (a) a colorant. The colored photosensitive composition according to any one of claims 1 to 3, which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB block copolymer and The BAB block copolymer includes an A block having at least one of a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and amine group. The colored photosensitive composition according to any one of claims 1 to 3, which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB block copolymer and The BAB block copolymer includes an A block having a quaternary ammonium salt group and an amine group in a side chain, and a B block having no quaternary ammonium salt group and an amine group. The colored photosensitive composition according to any one of claims 1 to 3, which contains at least one of an AB block copolymer and a BAB block copolymer as (f) a dispersant, the AB block copolymer and The BAB block copolymer includes an A block having an amine group without a quaternary ammonium salt group in the side chain, and a B block having no quaternary ammonium salt group and an amine group at the side chain. The coloring photosensitive composition according to any one of claims 1 to 3, which contains an oxime ester compound as (c) a photopolymerization initiator. A coloring spacer, which is formed at one time by the coloring photosensitive composition according to any one of claims 1 to 10 and has different heights. A color filter including the coloring spacer of claim 11. A liquid crystal display device includes a color filter according to claim 12. A one-time forming method of a colored spacer, using the colored photosensitive composition of any one of claims 1 to 10, and forming colored spacers of different heights at one time by a photolithography method.