KR101921369B1

KR101921369B1 - Colored photosensitive resin composition, colored spacer, color filter, and liquid crystal display device

Info

Publication number: KR101921369B1
Application number: KR1020147010655A
Authority: KR
Inventors: 리후아 페이; 요시타카 사와이; 마코토 후쿠이
Original assignee: 미쯔비시 케미컬 주식회사
Priority date: 2011-10-25
Filing date: 2012-10-24
Publication date: 2018-11-22
Also published as: JP5605481B2; TWI665520B; JP6421837B2; JP6143298B2; JP2019035970A; JP2014146018A; WO2013062011A1; KR20140093216A; TWI611263B; CN103890660A; JPWO2013062011A1; KR102007133B1; CN110262189A; JP2017146618A; CN103890660B; KR20180126090A; TW201324044A; TW201812453A

Abstract

Disclosure of the Invention A problem to be solved by the present invention is to provide a method for collectively forming colored spacers having different heights by a photolithography method in which a voltage maintaining ratio of a liquid crystal is ensured, To provide a photosensitive composition. The present invention provides a method for producing a photosensitive resin composition comprising the steps of: (a) preparing a photoresist composition containing a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, Relates to a colored photosensitive composition used for collectively forming different coloring spacers.

Description

TECHNICAL FIELD [0001] The present invention relates to a colored photosensitive composition, a colored spacer, a color filter, and a liquid crystal display device using the colored spacer,

The present invention relates to a colored photosensitive composition and the like. More particularly, the invention relates to a colored photosensitive composition which is preferably used for a colored spacer in a color filter such as a liquid crystal display, and a colored spacer, a color filter, and a liquid crystal display device formed thereby.

BACKGROUND ART A liquid crystal display (LCD) utilizes a property of switching the arrangement of liquid crystal molecules by turning on / off a voltage to a liquid crystal. On the other hand, many members forming the cells of the LCD are formed using photosensitive compositions typified by photolithography. The application range of the photosensitive composition tends to widen further in the future because it is easy to form a fine structure and easy to treat a substrate for a large screen.

However, in an LCD using a photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electrical characteristics of the photosensitive composition itself and the influence of impurities contained in the photosensitive composition, thereby causing problems such as display unevenness on the display. Particularly, in a liquid crystal display device which is closer to a liquid crystal layer, for example, a liquid crystal panel, which is used for maintaining a constant distance between two substrates, that is, a so-called columnar spacer, The effect is large.

Conventionally, when a spacer is used for a TFT-type LCD, a TFT as a switching element may malfunction due to light incident on the TFT. In order to prevent this, for example, Patent Document 1 discloses that the spacers are made light-shielding.

Recently, in manufacturing the spacers by the photolithography method, there has been proposed a method of collectively forming spacers having different heights in accordance with the change of the structure of the panel. Patent Document 2 discloses that by controlling the exposure amount and the residual film ratio, it is possible to realize the shapes and steps of spacers having different desired heights.

Japanese Unexamined Patent Publication No. 8-234212 Japanese Laid-Open Patent Publication No. 2009-31778

However, as described in Patent Document 1, it is conceivable to add a colorant or the like containing a pigment to the photosensitive composition in order to make the spacer shielding from light. However, when the colorant is added, the curability of the spacer layer There is a possibility that the electric characteristics are deteriorated due to the influence of impurities or the like derived from the pigment.

Patent Document 2 relates to a spacer to which a pigment is not added. When the pigment is applied to a batch formation of a coloring spacer to which a pigment is added, since the pigment absorbs light in the ultraviolet region contributing to photopolymerization, the light transmittance It has been found that it is difficult to attain characteristics such as the shape of the spacer having different desired heights, the control of the level difference, the adhesion with the substrate, and the like.

The present invention has been made in view of such circumstances. That is, a main object of the present invention is to provide a method for collectively forming colored spacers having different heights by photolithography, in which a voltage retention ratio of a liquid crystal is ensured and a desired shape is formed, a step is controlled, And to provide such an excellent colored photosensitive composition.

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

Still another object of the present invention is to provide a color filter having such a coloring spacer.

Still another object of the present invention is to provide a liquid crystal display device having such a color filter.

Still another object of the present invention is to provide a method for collectively forming colored spacers different in height by photolithography using such a colored photosensitive composition.

As a result of intensive studies on the above problems, the inventors of the present invention have found that by using a specific alkali-soluble resin and a dispersant, and by setting a weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound and a specific alkali- And the present invention has been accomplished. That is, the gist of the present invention is as follows.

(1) A photoresist composition containing a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, As the colored photosensitive composition used for collectively forming different coloring spacers,

(b) an alkali-soluble resin containing at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2)

(f) an acrylic block copolymer containing a nitrogen atom as a dispersant,

(d) the weight ratio of the (b) alkali-soluble resin to the ethylenically unsaturated compound is less than 7,

The total amount of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) relative to the total solid content in the colored photosensitive composition is 12% by weight or more.

&Lt; Alkali-soluble resin (A-1) >

A resin obtained by adding an?,? - unsaturated monocarboxylic acid or an?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety to the epoxy resin and further reacting the polybasic acid anhydride

&Lt; Alkali-soluble resin (A-2) >

Unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is added to the epoxy resin, and further, a polyhydric alcohol and a polybasic acid anhydride are reacted

[2] The colored photosensitive composition according to the above [1], wherein the total ratio 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 wt% or more.

[3] The colored photosensitive composition according to [1] or [2], wherein the content 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 [1] to [3], wherein the content of the colorant is 25% by weight or more based on the total solid content in the colored photosensitive composition.

[5] A pigment composition as described in any one of [1] to [4] above, which contains at least one of the following (1) red pigment and (2) And the coloring photosensitive composition described in any one of the above items.

(1) C.I. Pigment Red 177, 254

(2) C.I. Pigment Blue 15: 6 Blue pigment

(3) C.I. Pigment violet 23 purple pigment

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

(7) A method for producing a magnetic recording medium, comprising the steps of: (f) mixing an A block having at least one of a quaternary ammonium salt group and an amino group in a side chain and an AB block copolymer and a BAB block copolymer [1] to [6], wherein the coloring photosensitive composition contains at least one of the following components:

(8) A method for producing a magnetic recording medium, comprising the steps of: (f) mixing at least one of an A block having a quaternary ammonium salt group and an amino group in its side chain and an AB block copolymer and a BAB block copolymer having a quaternary ammonium salt group and an amino group- (1) to (6) above.

(9) The positive resist composition as set forth in any one of (1) to (8) above, wherein at least one of the A block having an amino group and the B block having no quaternary ammonium group and no amino group and having no quaternary ammonium salt group in the side chain, The colored photosensitive composition according to any one of the above [1] to [6], which contains one side.

[10] The colored photosensitive composition according to any one of [1] to [9], wherein the photopolymerization initiator (c) contains an oxime ester compound.

[11] A colored spacer different in height formed collectively by the colored photosensitive composition according to any one of [1] to [10].

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

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

[14] A method for collectively forming colored spacers having different heights by photolithography using the colored photosensitive composition according to any one of [1] to [10].

According to the present invention, in the method for collectively forming colored spacers having different heights by photolithography, it is possible to realize formation of a desired shape, control of a step, and adhesion with a substrate while securing the voltage holding ratio of the liquid crystal .

1 (A) and 1 (B) are views for explaining the shape of a substantially circular spacer pattern in the embodiment, where FIG. 1A is a plan view of a spacer pattern, to be.

Hereinafter, embodiments for carrying out the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention. Unless the gist of the present invention is deviated, Is not specified.

In the present invention, the term "(meth) acrylic acid" means both of acrylic acid and methacrylic acid, and the terms "(meth) acrylic", "(meth) acrylate" and " (Co) polymer "means that the polymer contains both a homopolymer (homopolymer) and a copolymer (copolymer), and" (acid) anhydride "," (anhydride) " Quot; acid " means containing both an acid and an anhydride thereof.

In the present invention, the term " monomer " is meant to refer to a so-called polymer material, and includes not only the monomer (monomer) but also the dimer, trimer and oligomer. Here, the term " total solid content " refers to the sum of all components other than the solvent contained in the colored photosensitive composition of the present invention.

[1] Batch formation method of coloring spacers having different heights

A method for collectively forming colored spacers having different heights by photolithography is a method characterized mainly by an exposure mask in an exposure process.

As the exposure mask, there is known a method of using an exposure mask having a light-shielding layer for blocking transmission of light and a plurality of apertures for transmitting light, wherein the average light transmittance of some of the apertures is smaller than the average light transmittance of the other apertures. This is because the opening portion having a light transmittance of 0% and a plurality of openings and having an average light transmittance smaller than that of the opening portion having the highest average light transmittance (normally, the light transmittance is 100% And a transmittance of more than 0% but less than 100%, preferably more than 5% and less than 50%). With this method, for example, in the case of a negative-type colored photosensitive composition, a difference in the degree of curing of the formed pattern is caused by a difference in average light transmittance between the intermediate transmission opening portion and the full transmission opening portion, After that, through the development and thermal curing process, the colored spacers having different heights can be formed.

[2] The colored photosensitive composition

The colored photosensitive composition according to the present invention comprises a photo-sensitive composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, A colored photosensitive composition for collectively forming colored spacers having different heights by a lithographic method,

(f) an acrylic block copolymer containing a nitrogen atom as a dispersant,

(A-1) and the alkali-soluble resin (A-2) relative to the total solid content in the colored photosensitive composition is 12% by weight or more.

&Lt; Alkali-soluble resin (A-1) >

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

&Lt; Alkali-soluble resin (A-2) >

A resin obtained by adding an?,? - unsaturated monocarboxylic acid or an?,? - unsaturated monocarboxylic acid ester having a carboxyl group to an ester moiety to an epoxy resin and further reacting a polyhydric alcohol and a polybasic acid anhydride.

[2-1] (a) Colorant

As the colorant, a pigment is usually used. As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment and a black pigment can be used. As the structure, various inorganic pigments and the like can be used in addition to organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, isoindolinone pigments, dioxazine pigments, indanthrene pigments and perylene pigments. Specific examples of usable pigments are shown below by pigment numbers. &Quot; C.I. Pigment Red 2 " and the like mean color index (C.I.).

As the red pigment, C.I. 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 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 48: 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, 81, : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, , 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. Of these, C.I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment Red 177, 209, 224, 254.

As the blue pigment, C.I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, , 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, Of these, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. Pigment Blue 15: 6.

As the green pigment, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, Of these, C.I. Pigment Green 7, 36 can be mentioned.

As the yellow pigment, C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: : 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: , 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, and 208, respectively. Of these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. Pigment Yellow 83, 138, 139, 150, and 180, respectively.

As the orange pigment, C.I. 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 them, C.I. Pigment Orange 38, and 71.

As the violet pigment, C.I. 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. Of these, C.I. Pigment Violet 19, 23, more preferably C.I. Pigment Violet 23 can be mentioned.

Examples of the black pigment include perylene black (BASF K0084, K0086), cyanine black, and first black HB (CI 26150).

The color photosensitive composition of the present invention may contain a single black color material or a black color material obtained by mixing red, green, and blue. These black coloring materials can be appropriately selected from among inorganic or organic pigments and dyes such as carbon black and titanium black, and they can be used singly or in combination.

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

MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900 and the like manufactured by Mitsubishi Chemical Corporation.

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

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

RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1020, RAVEN810, RAVEN850, RAVEN850, RAVEN850, RAVEN850, RAVEN850, RAVEN10, RAVEN10,

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

The colored photosensitive composition of the present invention is a colored photosensitive composition containing (a) a red pigment of the following (1) and at least one of the following blue pigment of the following (2) Is preferable from the viewpoint of light shielding property.

(1) C.I. Pigment Red 177, 254

(2) C.I. Pigment Blue 15: 6 Blue pigment

(3) C.I. Pigment violet 23 purple pigment

Among them, it is preferable to contain (1) and (2) from the viewpoint of securing the voltage holding ratio of the liquid crystal, controlling the level difference, and adhesion with the substrate. C.I. Pigment Red 254 and C.I. Pigment Blue 15: 6 is preferable from the viewpoint of improving the light shielding property in the visible light region.

In the colored photosensitive composition of the present invention, the content of the colorant (a) is preferably 35% by weight or less, more preferably less than 30% by weight based on the total solid content in the colored photosensitive composition. If it is 35% by weight or less, the difference (? H) between the height of the colored spacer pattern in the fully transparent opening portion and the height of the colored spacer pattern in the middle transparent opening portion is preferably large. If it is less than 30 wt%, the difference (DELTA H) between the height of the colored spacer pattern of the fully transparent opening portion and the height of the colored spacer pattern of the intermediate transparent opening portion exceeds 0.35 mu m. The preferred range is 5 wt% to 28 wt%, more preferably 10 wt% to 25 wt%. If the content of the colorant (a) is too large, the sensitivity of the colored photosensitive composition is lowered, and the shape or step of the spacer having a different desired height may not be formed. On the other hand, when the content ratio of the colorant is too small, sufficient light shielding property as the coloring spacer can not be secured in some cases.

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

The alkali-soluble resin (A-1) used in the present invention is obtained by adding an alpha, beta -unsaturated monocarboxylic acid or an alpha, beta -unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to the epoxy resin, Or by reacting a polybasic acid anhydride to give an alkali solubility. Such a reaction product has no epoxy group in chemical structure.

Examples of the epoxy resin to be used as the raw material include cresol novolak type epoxy resins, phenol novolak type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, trisphenol methane type epoxy resins, biphenyl novolac type epoxy resins, An epoxy resin, an adamantyl group-containing epoxy resin, and a fluorene-type epoxy resin, which are reaction products of epichlorohydrin with a cycloaliphatic epoxy resin, a cyclic epoxy resin, a reaction product of dicyclopentadiene with a phenol or cresol, .

The molecular weight of the epoxy resin is in the range of usually 200 to 200,000, preferably 300 to 100,000, as Mw, the weight average molecular weight (hereinafter referred to as " Mw ") in terms of polystyrene measured by gel permeation chromatography (GPC) . When the molecular weight is less than the above range, it may be difficult to obtain a preferable Mw alkali-soluble resin (A-1). On the other hand, when the molecular weight exceeds the above range, gelation There is a possibility that the production becomes difficult because it is easy to occur.

Examples of the?,? - unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid and the like, preferably acrylic acid and methacrylic acid, and acrylic acid is particularly preferable because it is rich in reactivity . Examples of the?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include acrylic acid-2-succinoyloxyethyl, acrylic acid-2-maleonyloxyethyl, Methacrylic acid-2-maleoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2- Hexahydrophthaloyloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like.

The addition reaction of an alpha, beta -unsaturated monocarboxylic acid or an alpha, beta -unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety with an epoxy resin can be carried out by a known method. The amount of the?,? - unsaturated monocarboxylic acid or?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of the epoxy group in the raw material epoxy resin, Preferably in the range of 0.7 to 1.1 equivalents. If the amount of the?,? - unsaturated monocarboxylic acid or the?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is too small, the amount of the introduced unsaturated group is insufficient, and the subsequent reaction with the polybasic acid anhydride may become insufficient . It is also not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount thereof is large, the?,? -Unsaturated monocarboxylic acid or its ester may remain as an unreacted material. In either case, there is a possibility that the curing property of the coating film is deteriorated.

Further, in the present invention, if the final resin structure is the same even without passing through the epoxy resin as a production step, it is also defined as a category of the alkali-soluble resin (A-1) in the present application. Examples thereof include a method of reacting a novolac resin with an epoxy compound containing an unsaturated group.

Examples of the polybasic acid anhydrides which are added to the product obtained by adding an alpha, beta -unsaturated monocarboxylic acid to the epoxy resin or an alpha, beta -unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety are maleic anhydride, Phthalic acid, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, anhydrous pyromellitic acid, anhydrous trimellitic acid, benzophenonetetracarboxylic acid dianhydride, anhydrous methylhexahydrophthalic acid, anhydroendomethylene tetrahydrophthalic acid, anhydrous chlorodic acid, Methyl tetrahydrophthalic acid, biphenyltetracarboxylic acid dianhydride and the like. Of these, preferred are maleic anhydride, succinic anhydride, phthalic anhydride, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, anhydrous pyromellitic acid, anhydrous tri Mellitic acid, biphenyltetracarboxylic acid dianhydride, and particularly preferred tin Water is a tetrahydrophthalic acid anhydride and biphenyltetracarboxylic acid dianhydride.

With respect to the addition reaction of the polybasic acid anhydride, a known method may be used. The amount of addition of the polybasic acid anhydride is preferably in the range of 10 mgKOH / g to 150 mgKOH / g, more preferably in the range of 20 mgKOH / g to 140 mgKOH / g in the acid value of the resulting epoxy acrylate resin Do. When the acid value is less than the above range, alkali developability becomes insufficient. When the acid value exceeds the above range, the curing performance tends to be inferior.

The weight average molecular weight (Mw) of the alkali-soluble resin (A-1) used in the present invention in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1,500 or more, preferably 2,000 or more, Preferably 50000 or less, preferably 30000 or less, more preferably 10000 or less. If the weight average molecular weight of the alkali-soluble resin (A-1) is too low, the sensitivity tends to decrease. If the weight-average molecular weight is too large, the solubility in the developer may be insufficient.

The alkali-soluble resin (A-2) used in the present invention is obtained by adding an?,? -Unsaturated monocarboxylic acid or an?,? - unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to the epoxy resin, Is reacted with a polyhydric alcohol and a polybasic acid anhydride.

All of the components other than the synthetic method and polyhydric alcohol used for the synthesis of the alkali-soluble resin (A-1) can be used for the synthesis of the alkali-soluble resin (A-2). The alkali-soluble resin (A-2) is usually prepared by adding an alpha, beta -unsaturated monocarboxylic acid or an alpha, beta -unsaturated monocarboxylic acid ester having a carboxyl group to the ester moiety to an epoxy resin, , A polyhydric alcohol and a polybasic acid anhydride, and warming them. In this case, the mixing order of the polyhydric alcohol and the polybasic acid anhydride is not particularly limited.

Examples of polyhydric alcohols used in the synthesis of the alkali-soluble resin (A-2) include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3- It is preferable that the polyhydric alcohol is one or more polyhydric alcohols.

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

If the amount of the polyhydric alcohol is too small, the effect is insufficient. If the amount is too large, there is a possibility of thickening or gelation. Therefore, an epoxy resin component and an?,? - unsaturated monocarboxylic acid or an?,? - unsaturated monocarboxylic acid having a carboxyl group in the ester moiety Is usually about 0.01 to 0.5 parts by weight, preferably about 0.02 to 0.2 parts by weight, with respect to the reactant with the carboxylic acid ester component.

The acid value of the alkali-soluble resin (A-2) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more. When the acid value is less than 10 mgKOH / g, the developability may be insufficient. On the other hand, if the acid value is too high, there is a problem in the alkali resistance of the colored photosensitive composition (that is, roughening of the pattern surface or reduction in film is caused by the alkaline developer). Therefore, the acid value is preferably 200 mgKOH / g or less , And more preferably not more than 150 mgKOH / g.

The weight average molecular weight (Mw) of the alkali-soluble resin (A-2) in terms of polystyrene determined by gel permeation chromatography (GPC) is preferably 1,500 or more, and more preferably 2,000 or more. Further, it is preferably 20,000 or less, more preferably 10,000 or less. If the weight-average molecular weight is too small, there is a possibility that the sensitivity, the coating film strength and the alkali resistance are disadvantageous. If the weight average molecular weight is too large, there is a problem in developing property and re-solubility.

The total ratio of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) to the total solid content in the colored photosensitive composition of the present invention is 12% by weight or more, preferably 20% Is generally 30% by weight or more, usually 70% by weight or less, preferably 60% by weight or less, and more preferably 50% by weight or less. If the proportion of the alkali-soluble resin is higher than this range, the developability is deteriorated and the proportion of the pigment is too small, so that the required light-shielding property can not be secured. On the other hand, if the ratio is too small, .

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 according to the present invention is a compound capable of generating a radical which polymerizes an ethylenic unsaturated group by ultraviolet rays or heat.

Specific examples of the photopolymerization initiator usable in the present invention are listed below.

(Trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s- Bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloro Halomethylated triazine derivatives such as trimethylsilyl) -s-triazine;

Halomethylated oxadiazole 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 the like;

Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether;

Anthraquinone derivatives such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone;

Benzanthrone derivatives;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone and 2-carboxybenzophenone;

Hydroxy-2-methylphenylpropanone, 1-hydroxy-1- (2-hydroxyphenyl) acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, Methyl-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '- (methylthio) phenyl) Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone;

Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-di Thioxanthone derivatives such as isopropylthioxanthone;

benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;

Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine;

Phenazine derivatives such as 9,10-dimethylbenzphenazine;

Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di- cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluoropheny-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6 Di-cyclopentadienyl-Ti-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluoro Di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis , Titanocenes such as 6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro- Derivatives;

2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisobutyl benzoate, 4-diethylamino acetophenone , 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino- -Diethylaminobenzoyl) coumarin, and 4- (diethylamino) chalcone;

As the photopolymerization initiator, in particular, oxime derivatives (oxime compounds and ketoxime compounds) are effective in terms of sensitivity, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, Therefore, oxime derivatives (oxime compounds and ketoxime compounds) having such excellent sensitivity are particularly useful.

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

[Chemical Formula 1]

(Wherein ^(2), R 2 An alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, a cycloalkanoyl group having 3 to 20 carbon atoms, An alkoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminoalkylcarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonylamino group having 7 to 20 carbon atoms A heteroaryl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

(2)

(In the formula (3), R &^lt; ^1a ^> Represents a hydrogen atom or an optionally substituted 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, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxy group having 8 to 20 carbon atoms A heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, An aryloxy group having 7 to 20 carbon atoms, a heteroaryloxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

R ^1b Represents any substituent containing an aromatic ring or a heteroaromatic ring.

In addition, R ^< Is to form a ring with R ^1b, the linking group is an alkylene group, polyethylene group having 1 to 10 carbon atoms which may have a substituent _{(- (CH = CH) r} -), poly ethynyl group (- (C≡ C) _r -), or a group formed by combining these groups (and r is an integer of 0 to 3).

R ^2a An alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, a cycloalkanoyl group having 3 to 20 carbon atoms, An alkoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkanoyl group having 3 to 20 carbon atoms, an aminocarbonyl group having 2 to 10 carbon atoms, an aryloyl group having 7 to 20 carbon atoms , A heteroaryl chloro group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

R ² in the general formula (2) and R ^2a in the general formula (3) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, And a cycloalkanoyl group having 3 to 8 carbon atoms.

The R ^1a in the general formula (3) is preferably an unsubstituted methyl group, an ethyl group, a propyl group or a propyl group substituted with an N-acetyl-N-acetoxyamino group.

The R ^1b in the general formula (3) is preferably a substituted or unsubstituted carbazoyl group, a thioxanthonyl group which may be substituted, or a phenylsulfide group which may be substituted.

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

(3)

[Chemical Formula 4]

Examples of the ketoxime compound include a compound 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).

[Chemical Formula 5]

(In the above general formula (4), R < ⁴ > Is R ² in the general formula (2) And agreement.)

[Chemical Formula 6]

(In the above general formula (5), R < ^3a > Each independently represent a phenyl group, 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, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxy group having 8 to 20 carbon atoms An alkylthioalkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an aminoalkyl group having 3 to 20 carbon atoms, A cycloalkanoyl group having 3 to 8 carbon atoms, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryl group having 7 to 20 carbon atoms Oxycarbonyl group.

R ^3b Represents any substituent containing an aromatic ring or a heteroaromatic ring.

Also, R ^3a Is R and form a ring with ^3b, the linking group is an alkylene group, polyethylene group having 1 to 10 carbon atoms which may have a substituent _{(- (CH = CH) r} -) - (C≡, poly group (ethynyl C) _r -), or a group formed by combining these groups (and r is an integer of 0 to 3).

R ^4a An alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms An alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

The R ⁴ in general formula (4) and R ^4a in general formula (5) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, A cycloalkanoyl group having 3 to 8 carbon atoms, and an aryloyl group having 7 to 20 carbon atoms.

As R < ^3a > in the general formula (5), an unsubstituted ethyl group, propyl group, butyl group, or ethyl group or propyl group substituted by methoxycarbonyl group can be exemplified.

As R ^3b in the general formula (5), a carbazoyl group which may be optionally substituted, or a phenylsulfide group which may be substituted may be mentioned.

Specific examples of the keto oxime ester compound preferred in the present invention include the compounds exemplified below, but the compounds are not limited to these compounds at all.

(7)

These oxime and keto oxime ester compounds are known compounds themselves and are a kind of a series of compounds described, for example, in JP-A 2000-80068 and JP-A 2006-36750.

These photopolymerization initiators may be used singly or in combination of two or more.

The proportion of the photopolymerization initiator in the light-shielding photosensitive resin composition of the present invention is generally 0.4 to 15% by weight, preferably 0.5 to 10% by weight, based on the total solid content. If the ratio of the photo polymerization initiator is higher than this range, the developability tends to decrease. On the other hand, if the proportion is too small, the desirable voltage holding ratio, shape of the colored spacer, and step can not be formed.

The colored photosensitive composition according to the present invention is characterized in that the weight ratio of the alkali-soluble resin to the ethylenically unsaturated compound is less than 7. In this case, the alkali-soluble resin means the total of all the 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, more preferably 2 or more, preferably 6 or less, and still more preferably 5 or less. If it is 7 or more, necessary steps can not be formed, and if it is too small, developability may be deteriorated. When a large amount of an alkali-soluble resin having a long dissolving time for a developing solution is used, the developing property may be lowered even if it is 7 or more.

[2-4] (d) Ethylenically unsaturated compound

The photopolymerization initiator is used together with an ethylenically unsaturated compound.

The ethylenically unsaturated compound used herein means a compound having at least one ethylenic unsaturated bond in the molecule, but it is preferable that the ethylenic unsaturated compound is polymerized, crosslinked, and the difference between the solubility of the developer in the exposed portion and the non- (Meth) acryloyloxy group. The (meth) acryloyloxy group is preferably a (meth) acrylate compound derived from a (meth) acryloyloxy group, and the unsaturated bond is more preferably a compound having two or more ethylenic unsaturated bonds in the molecule.

In addition, the use of a compound having three or more ethylenic unsaturated bonds in the molecule is preferable in terms of voltage holding ratio.

Examples of the compound having at least one ethylenic unsaturated bond in the molecule include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid and citraconic acid, , (Meth) acrylonitrile, (meth) acrylamide, and styrene.

Representative examples of the compound having two or more ethylenically unsaturated bonds in the molecule include esters of an unsaturated carboxylic acid and a polyhydroxy compound, phosphates containing a (meth) acryloyloxy group, hydroxy (meth) acrylate compounds and Urethane (meth) acrylates of polyisocyanate compounds and epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds.

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

Specific examples of the sugar alcohol include ethylene glycol, polyethylene glycol (adduct 2 to 14), propylene glycol, polypropylene glycol (adduct 2 to 14), trimethylene glycol, tetramethylene glycol , Hexamethylene glycol, trimethylol propane, glycerol, pentaerythritol, dipentaerythritol and the like.

The reaction product of the unsaturated carboxylic acid and the alkylene oxide adduct of the sugar alcohol; the sugar alcohol is the same as described above. Specific examples of the alkylene oxide adducts include ethylene oxide adducts and propylene oxide adducts.

Reaction products of unsaturated carboxylic acid and alcohol amine: Specific examples of the alcohol amines include diethanolamine, triethanolamine and the like.

Specific examples of esters of unsaturated carboxylic acid and polyhydroxy compound are as follows.

Acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide adduct tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and the same crotonate, isocroton Nate, maleate, itaconate, citraconate, and the like.

Examples of other esters of an unsaturated carboxylic acid and a polyhydroxy compound include unsaturated carboxylic acids and aromatic polyhydroxy compounds such as hydroquinone, resorcin, pyrogallol, bisphenol F, and bisphenol A, or their ethylene oxide adducts . &Lt; / RTI > Specific examples include bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate] The reaction product of the same unsaturated carboxylic acid with a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, for example, a reaction product of tris (2-hydroxyethyl) isocyanurate with di (Meth) acrylate, tri (meth) acrylate and the like, reaction products of an unsaturated carboxylic acid and a polyvalent carboxylic acid and a polyhydroxy compound, such as a condensate of (meth) acrylic acid, phthalic acid and ethylene glycol, ) Condensates of acrylic acid, maleic acid and diethylene glycol, condensates of (meth) acrylic acid, terephthalic acid and pentaerythritol, condensates of (meth) acrylic acid, adipic acid, butanediol and glycerin, There.

As the (meth) acryloyloxy group-containing phosphates, those represented by the following general formulas (6), (7) and (8) are preferable.

[Chemical Formula 8]

(Of the formulas (6), (7) and (8), R ¹⁰ P and p 'are an integer of 1 to 25, and q is 1, 2, or 3.)

(Meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] oxyacetate, and the like are preferable. Phosphate, (meth) acryloyloxyethylene glycol phosphate, and the like, each of which may be used alone or as a mixture.

Examples of the urethane (meth) acrylates of the hydroxy (meth) acrylate compound and the polyisocyanate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylol ethane tri (Meth) acrylate, and alicyclic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane, cyclohexane diisocyanate, dimethyl cyclohexane diisocyanate, Alicyclic polyisocyanates such as 4,4-methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, and bicycloheptane triisocyanate; aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanate phenyl) thiophosphate; Isocyanate, isocyanurate, etc. And a reaction product with a polyisocyanate compound such as cyclic polyisocyanate.

Examples of such resins include UA-306A, UA-MC340H, UA-MC340H, U6LPA, and the like, which are available from Shin Nakamura Chemical Co.,

Among them, a compound having at least 4 urethane bonds [-NH-CO-O-] and at least 4 (meth) acryloyloxy groups in one molecule is preferable, and the compound is, for example, pentaerythritol, A compound obtained by reacting a compound having four or more hydroxyl groups in a molecule such as polyglycerin with a diisocyanate compound such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, or the like, or a compound obtained by reacting ethylene glycol Durenate 22A-75PX ", durenate 21S-75E", durenate 18H-75E "manufactured by Asahi Chemical Industry Co., Ltd., 70B ", and other duct types such as" DURANATE P-301-75E ", DURANATE E-402-90T and DURANATE E-405-80T. Preferably at least 6 isocyanate groups in a molecule, such as a compound obtained by reacting a compound having three or more isocyanate groups in a molecule or a compound obtained by polymerizing or copolymerizing isocyanate ethyl (meth) acrylate or the like (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Acrylate and dipentaerythritol penta (meth) acrylate, which have at least one hydroxyl group and at least two, preferably at least three (meth) acryloyloxy groups per molecule have.

Examples of the epoxy (meth) acrylates of (meth) acrylic acid or hydroxy (meth) acrylate compounds and polyepoxy compounds include (meth) acrylic acid, or hydroxy (meth) (Poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, (Poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, (O-, m-, p-) cresol novolak polyepoxy compounds, bisphenol compounds such as bisphenol Aromatic polyepoxy compounds such as A polyepoxy compounds and bisphenol F polyepoxy compounds, sorbitan polyglycidyl ether, triglycidyl isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate. A reaction product with a polyepoxy compound such as a heterocyclic polyepoxy compound, and the like.

As other ethylenically unsaturated compounds, for example, allyl esters such as (meth) acrylamides such as ethylenebis (meth) acrylamide and diallyl phthalate, and vinyl group-containing compounds such as divinyl phthalate , Thioether bond-containing compounds in which the ether bond of the ether bond-containing ethylenically unsaturated compound is sulphated by sulfur pentasulfide or the like to change it to a thioether bond to improve the crosslinking speed, and, for example, Japanese Patent Publication No. 3164407 (Meth) acrylate compound and a silica sol having a particle diameter of 5 to 30 nm (for example, isopropanol-dispersed organosilica sol (manufactured by NISSAN CHEMICAL INDUSTRIES, LTD., IPA-ST ), Methyl ethyl ketone-dispersed organosilica sol ("MEK-ST" manufactured by Nissan Chemical Industries, Ltd.), methyl isobutyl ketone-dispersed organosilica sol Manufactured by Mitsubishi Chemical Corporation, "MIBK-ST")) with an isocyanate group or a mercapto group-containing silane coupling agent to react and bond the ethylenically unsaturated compound with a silica sol via a silane coupling agent, And a compound having improved strength and heat resistance.

In the present invention, the ethylenically unsaturated compound is preferably an ester (meth) acrylate or a urethane (meth) acrylate, and among these, dipentaerythritol hexa (meth) acrylate, dipentaerythritol And pentafunctional (meth) acrylate.

These ethylenically unsaturated compounds may be used alone or in combination of two or more.

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

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

[2-5] (e) Solvent

Each component contained in the colored photosensitive composition of the present invention as described above is usually used as a solution of a colored photosensitive composition by dissolving or dispersing in a solvent.

Examples of the solvent to be used herein include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n But are not limited to, hexane, hexane, hexane, hexane, hexane, hexane, hexane, octane, , &Lt; / RTI > 1 and No. 2. (N, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride , Ethyleneglycol diethylether, ethylorthoformate, methoxymethylpentanone, methylbutylketone, methylhexylketone, methylisobutyrate, benzonitrile, ethylpropionate, methylcellosolve acetate, methyl isoamyl ketone , Methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate , Propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, Propylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol, 3-methoxybutanol, propylene glycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, propyleneglycol monomethyl ether, 3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate, etc. . These solvents may be used singly or in combination of two or more kinds.

In the colored photosensitive composition of the present invention, the content of the solvent is not particularly limited, but is usually 90% by weight or less, usually 60% by weight or more, more preferably 60% by weight or more, It is preferably at least 70% by weight. That is, in the colored photosensitive composition of the present invention, it is preferable that the concentration of the total solid content is usually 10% by weight or more, usually 40% by weight or less, particularly 30% by weight or less.

[2-6] (f) Dispersing agent

In the photosensitive resin composition of the present invention, a dispersant is used for improving the dispersibility of the colorant and improving the dispersion stability.

In the present invention, an acrylic block copolymer containing a nitrogen atom is used as a dispersant. The nitrogen-containing acrylic block copolymer having such a nitrogen atom has affinity for the surface of the colorant, and the portion other than the nitrogen atom enhances the affinity for the medium, thereby contributing to improvement of dispersion stability as a whole .

The performance of the dispersant is the adsorption behavior on the solid surface. The reason why the block copolymer has excellent adsorption behavior is that the detailed mechanism is unclear, but the following is presumed.

That is, in the case of a typical random copolymer, the probability that the monomers constituting the copolymer are stably arranged in the copolymer steric and / or electrically is increased. Since the moiety (molecule) in which the monomer is stably placed is sterically and / or electrically stable, there is a case where the moiety is rather obstructed when adsorbed to the colorant. On the other hand, in a resin such as a block copolymer in which the molecular arrangement is controlled, a portion that hinders adsorption of the dispersant can be disposed at a position away from the adsorbing portion of the pigment and the dispersant. In other words, the adsorption portion of the colorant and the dispersant may be provided with an optimum portion for adsorption, and the portion to which solvent affinity is required may be disposed at a portion suitable for adsorption. Particularly, the dispersion of the coloring material containing the coloring agent having a small crystallite size is presumed to affect the good dispersibility of the molecular arrangement.

The acrylic block copolymer containing a nitrogen atom is preferable in that the colorant used in the present invention can be dispersed very efficiently. The reason for this is unclear, but it is presumed that the molecular arrangement is controlled, so that the structure which becomes a trouble when the dispersant is adsorbed on the colorant is small. As the acrylic block copolymer, at least one of an A block having at least one of a quaternary ammonium group and an amino group in a side chain and an AB block copolymer and a BAB block copolymer composed of a B block having no quaternary ammonium group and an amino group .

When the A block has a quaternary ammonium salt group, the quaternary ammonium salt group is preferably -N ⁺ R ²¹ R ²² R ²³ M ^- (provided that R ²¹ , R ²² and R ²³ Each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, R ²¹ , R ²² and R ²³ May be bonded to each other to form an annular structure. And M ^- indicates counter no.). The quaternary ammonium salt group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

-N ⁺ R ²¹ R ²² R ²³ , R ²¹ , R ²² and R ²³ For example, a nitrogen-containing heterocyclic ring having 5 to 7 atomic rings, or a condensed ring formed by condensing two of these rings. The nitrogen-containing heterocyclic ring preferably has no aromaticity, and is more preferably a saturated ring. Specifically, for example, the following can be mentioned. These cyclic structures may further have a substituent.

[Chemical Formula 9]

(Wherein R represents any one of R ²¹ to R ²³ ).

More preferable examples of R ²¹ to R ^{23 in} -N ⁺ R ²¹ R ²² R ²³ include an alkyl group having 1 to 3 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a benzyl group which may have a substituent .

As the A block having a quaternary ammonium salt group, it is particularly preferable to contain a partial structure represented by the following general formula (VI).

[Chemical formula 10]

(In the formula (VI), R ²¹ , R ²² , R ²³ Each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, 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), each of the hydrocarbon groups represented by R ²¹ , R ²² and R ²³ is preferably independently a substituent having an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 20 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, benzyl and phenyl. Among them, a methyl group, an ethyl group, a propyl group and a benzyl group are preferable.

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 - in which R ²⁵ and R ²⁶ 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 Each independently represent an alkylene group), and the like, preferably -COO-R ²⁶ -.

Examples of M ^{- in the} counterion include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- and the like.

The partial structure containing the specific quaternary ammonium salt group may contain two or more species in one A block. In this case, the partial structure containing two or more quaternary ammonium salt groups may be contained in the A block in either of random copolymerization or block copolymerization. Further, a partial structure not containing the quaternary ammonium salt group may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylate ester-based monomer described later.

The content of the quaternary ammonium salt group-containing partial structure in the A block is preferably 0 to 50% by weight, and more preferably 0 to 20% by weight. However, the quaternary ammonium salt group- Most preferably not contained.

In addition, the A block of the acrylic block copolymer described above may have an unreacted tertiary amino group which is not quaternized.

When the A block has an amino group, the amino group may be any of 1 to 3 classes. The content of the monomer having a primary to tertiary amino group is preferably 20 mol% or more, and more preferably 50 mol% or more, in the monomer composition constituting the acrylic block copolymer.

The amino group may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

The above-mentioned primary to tertiary amino group is preferably -NR ⁴¹ R ⁴² (Provided that R ⁴¹ and R ⁴² each independently represent a cyclic or a chained alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent) Preferable examples of the partial structure (repeating unit) containing it include a structure represented by the following general formula.

(11)

(Provided that R ⁴¹ and R ⁴² R < ⁴¹ > and R < ^{42 &} , And R ⁴³ Is an alkylene group having 1 or more carbon atoms, R < ⁴⁴ > Represents a hydrogen atom or a methyl group.)

Among them, R ⁴¹ and R ⁴² Is preferably a methyl group, and R < ⁴³ > Is preferably a methylene group or an ethylene group, 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 is particularly preferably used.

[Chemical Formula 12]

( ^Wherein R ⁴⁴ Is a tactic and an agreement.)

The amino group-containing partial structure may be contained in two or more A blocks. In this case, the two or more amino group-containing partial structures may be contained in the A block in either of random copolymerization and block copolymerization. In addition, a partial structure containing no amino group may be partially contained in the A block. Examples of the partial structure include a partial structure derived from a (meth) acrylate monomer. The content of the amino group-free partial structure in the A block is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. However, the amino group-free partial structure is not contained in the A block, desirable.

The A block may have either a quaternary ammonium salt group or an amino group, or both. For the solvent having a low polarity, the solubility of the quaternary ammonium salt group is low and the solubility of the amino group is high. Therefore, when a solvent having a low polarity is used in a large amount in the resist, from the viewpoint of improving the solubility of the dispersing agent in the resist solvent, it is preferable that the A block has a quaternary ammonium group and an amino group, , And it is more preferable to have an amino group without having a quaternary ammonium 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 quaternary ammonium salt group and the amino group described above and is composed of a monomer copolymerizable with the monomer constituting the above-described A block. The B block has a function of stabilizing the pigment adsorbed on the dispersing agent in the solvent since the B block is a hydrophilic part having no nitrogen atom-containing functional group which becomes a pigment adsorber and has affinity for a solvent.

Examples of the B block include styrene-based monomers such as styrene and? -Methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) (Meth) acrylate, glycidyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate-based monomers such as (meth) acrylic acid chloride, (meth) acrylate-based monomers such as (meth) acrylamide, N- (Meth) acrylamide-based monomers such as dimethylacrylamide and N, N-dimethylaminoethyl acrylamide, vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, N-methacryloylmorphol Lin, there may be mentioned a polymer structure obtained by copolymerizing a co-monomer, such as.

As the B block, it is particularly preferable to contain a partial structure derived from a (meth) acrylic acid ester-based monomer represented by the following formula (VIII).

[Chemical Formula 13]

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

The partial structure derived from the (meth) acrylate monomer may contain two or more species in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block not containing a quaternary ammonium group, each partial structure may be contained in the B block in any of random copolymerization and block copolymerization.

When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate-based monomer, the content of the partial structure other than the (meth) acrylate-based monomer in the B block is preferably 0 to 99 wt% %, More preferably 0 to 85 wt%.

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

Examples of the living polymerization method include anion living polymerization method, cationic living polymerization method, and radical living polymerization method. For example, the method described in JP-A-2007-270147 can be mentioned.

In addition, the amine value of the acrylic block copolymer is usually about 1 to 300 mgKOH / g in terms of effective solid content, but the preferable range is different between the case where the A block has a quaternary ammonium salt group and the case where it is not. Also, the amine value is a value expressed in mg of KOH corresponding to the molar equivalent of the acid required to neutralize the amino group in 1 g of the copolymer.

That is, in the AB block copolymer and the BAB block copolymer according to the present invention, when the A block has a quaternary ammonium salt group, the amount of the quaternary ammonium salt group in 1 g of the copolymer is preferably from 0.1 to 10 mmol Outside this range, there are cases in which good heat resistance and dispersibility can not be combined.

The block copolymer usually contains an amino group generated during the production process. The amine value of the block copolymer is usually about 1 to 100 mgKOH / g, preferably about 1 to 80 mgKOH / g, Is 1 to 50 mgKOH / g.

When the quaternary ammonium salt group is not contained in the A block, the amine value of the copolymer is usually about 50 to 300 mgKOH / g, preferably about 50 to 200 mgKOH / g, more preferably about 80 mgKOH / g Or more and 150 mgKOH / g or less, and more preferably 90 to 150 mgKOH / g.

Generally, the acid value of such an acrylic block copolymer is preferably 100 mgKOH / g or less, and more preferably 50 mgKOH / g or less, 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 in terms of the weight average molecular weight (Mw) in terms of polystyrene measured by GPC. When the molecular weight of the acrylic block copolymer is too low, dispersion stability is deteriorated. When the molecular weight is too large, developability and resolution tend to decrease.

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

In the present invention, the content of the acrylic block copolymer containing nitrogen atom is usually 5% by weight or more and 90% by weight or less, preferably 5% by weight or more and 60% by weight or less, more preferably 5% % Or more and 40 wt% or less. When the content of the nitrogen-containing acrylic block copolymer is too small, sufficient dispersibility may not be obtained. When the content is too large, the proportion of the other components is decreased, and the voltage holding ratio is lowered. On the other hand, May not be formed.

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

Examples of the dispersing agent used in combination include a urethane-based dispersant, a polyallylamine-based dispersant, a dispersant comprising a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene-diester- , A polyester phosphoric acid-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified polyester-based dispersant.

It is preferable that the colored photosensitive composition of the present invention is used in combination with a dispersion auxiliary agent for improving the dispersion stability of the colorant. Here, the dispersion auxiliary means a pigment derivative or the like for enhancing the dispersibility of the colorant.

Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, Pyrrole, and dioxazine. Of these, quinophthalone is preferable. Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amide group, etc. directly to the pigment skeleton or an alkyl group, , And preferably a sulfonic acid group. These substituents may be substituted by plural substituents on one pigment skeleton.

Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, an anthraquinone sulfonic acid derivative, a quinacridone sulfonic acid derivative, a diketopyrrolopyrrole sulfonic acid derivative, and a dioxazine sulfonic acid derivative.

These pigment derivatives may be used singly or in combination of two or more kinds.

When a pigment derivative is used, the amount of the pigment to be used is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.1 to 5% by weight based on the pigment .

[2-7] Other components

The light-shielding photosensitive resin composition of the present invention may further contain a polymerization accelerator, a sensitizer, a surfactant, a photoacid generator, a crosslinking agent, an adhesion improver, a plasticizer, a storage stabilizer, a surface protective agent, an organic carboxylic acid, A carboxylic acid anhydride, a phenomenon improving agent, a thermal polymerization inhibitor, and the like.

[2-7-1] Photo acid generator

The photoacid generator is a compound capable of generating an acid by ultraviolet rays, and a crosslinking agent such as a melamine compound, for example, is caused by the action of an acid generated when exposure is carried out, thereby causing the crosslinking reaction to proceed. Of these photoacid generators, those having a high solubility in a solvent, particularly a solvent used in a colored photosensitive composition are preferred, and examples thereof include diphenyliodonium, ditolyl iodonium, phenyl (p-anisyl) iodine Iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl ( diaryl iodonium such as p-tolyl) iodonium and p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium such as triphenylsulfonium chloride, bromide, or boronate, hexafluoro (Pentafluorophenyl) borate salts and the like, sulfonium organic boron complexes such as diphenylphenazylsulfonium (n-butyl) triphenylborate, and the like, Alternatively, 2-methyl-4,6-bist trichloromethyl triazine, And triazine compounds such as 2- (4-methoxyphenyl) -4,6-bistricloromethyltriazine, but are not limited thereto.

[2-7-2] Crosslinking agent

In the colored photosensitive composition of the present invention, a crosslinking agent may be further added, and for example, a melamine or guanamine-based compound may be used. Examples of the crosslinking agent include melamine or guanamine-based compounds represented by the following general formula (XI).

[Chemical Formula 14]

(Wherein R ⁶¹ Is -NR ⁶⁶ R ⁶⁷ Or aryl, and R < ⁶¹ > -NR ⁶⁶ R ⁶⁷ R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ One, and R ⁶¹ In the case of this aryl, R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ One of the -CH ₂ OR ⁶⁸ And the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently of one another are hydrogen or -CH ₂ OR ⁶⁸ Group, wherein R < ⁶⁸ > Represents hydrogen or alkyl.)

Here, aryl is typically phenyl, 1-naphthyl or 2-naphthyl, and phenyl or naphthyl of these may be substituted with substituents such as alkyl, alkoxy, halogen and the like. The alkyl and alkoxy may each have about 1 to 6 carbon atoms. The alkyl represented by R ⁶⁸ is preferably methyl or ethyl, especially methyl.

Examples of the melamine compound corresponding to the formula (XI), that is, the compound represented by the formula (XI-1) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethyl Melamine, tetramethoxymethyl melamine, hexaethoxymethyl melamine, and the like.

[Chemical Formula 15]

(Wherein R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ For one of the aryl group include R ^62, R ^63, R ⁶⁴ and R ⁶⁵ One of the -CH ₂ OR ⁶⁸ And the rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ independently of one another are hydrogen or -CH ₂ OR ⁶⁸ Group, and R < ⁶⁸ > Represents hydrogen or alkyl.)

In addition, a guanamine-based compound corresponding to the formula (XI), that is, R ⁶¹ The aryl compound includes tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine, and the like.

A crosslinking agent having a methylol group or a methylol alkyl ether group may also be used. An example is given below.

(Hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl- -1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether, dimethyloltrimethyleneurea or its dimethyl ether, 3,5-bis (hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (also known as dimethyloluron) or a dimethyl ether thereof, tetramethylolglyoxaldiurene or tetramethyl ether thereof.

These crosslinking agents may be used alone or in combination of two or more. When the crosslinking agent is used, the amount is preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight, based on the total solid content of the light-shielding photosensitive resin composition.

[2-7-3] Adhesion improving agent

The light-shielding photosensitive resin composition of the present invention may contain an adhesion improving agent in order to sufficiently adhere fine lines or dots.

As the adhesion improver, a compound containing a nitrogen atom, a compound containing a phosphoric acid group, a silane coupling agent and the like are preferable, and as the compound containing a nitrogen atom, for example, diamines (Japanese Patent Application Laid-Open No. 11-184080 Enhancer, etc.) and azoles are preferable. Of these, azoles are preferable, and imidazoles (adhesion improvers described in Japanese Patent Application Laid-Open No. 9-236923, etc.), benzoimidazoles, benzotriazoles (in Japanese Unexamined Patent Application Publication No. 2000-171968 Enhancers, etc.) are preferable, and imidazoles and benzimidazoles are most preferable. Among these, from the viewpoint that blackening hardly occurs and adhesion can be greatly improved, it is preferable to use 2-hydroxybenzoimidazole, 2-hydroxyethylbenzoimidazole, benzoimidazole, 2-hydroxyimidazole, imidazole, 2 -Mercaptoimidazole and 2-aminoimidazole are preferable, and 2-hydroxybenzoimidazole, benzimidazole, 2-hydroxyimidazole and imidazole are particularly preferable. As the type of silane coupling agent, various types such as epoxy type, methacryl type, and amino type can be used, and in particular, an epoxy type silane coupling agent is preferable.

These may be used singly or in combination of two or more.

When these adhesion improvers are compounded, the compounding ratio thereof is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, based on the total solid content of the colored photosensitive composition, although it varies depending on the kind of the adhesion- . If it is less than this range, sufficient adhesion improving effect may not be obtained, and if it is too large, developability may be deteriorated.

[2-7-4] Increasing dye

As the sensitizing dye, for example, Japanese Patent Application Laid-Open Nos. 4-221958 and 4-219756, Japanese Laid-Open Patent Application No. 3-239703, Japanese Laid-Open Patent Application No. 5-289335 , 3-ketocumarin compounds described in Japanese Patent Application Laid-Open Nos. 3-239703 and 5-289335, pyromethene compounds described in Japanese Patent Application Laid-Open No. 6-19240 Pigments, and in addition, JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A- 52-112681, 58-15503, 60-88005, 59-56403, 60-69, JP-A-60-88005, JP-A- 57-168088, JP-A-5-107761, JP-A-5-210240, And a dye having a dialkylaminobenzene skeleton described in JP-A-4-288818.

These may be used singly or in combination of two or more.

When the sensitizing dye is blended, the content 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 range, the effect of increasing or decreasing may not be exhibited. If too much, the developability may be lowered.

[2-7-5] Surfactant

As the surfactant, one or more of anionic, cationic, nonionic, amphoteric surfactants and the like can be used. However, from the viewpoint that there is little possibility of adversely affecting all the properties, a nonionic surfactant Is preferably used. In addition, fluorine-based or silicon-based ones are effective in terms of coating properties.

The blending ratio of the surfactant is generally 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, and most preferably 0.03 to 0.3% by weight based on the total solid content in the colored photosensitive composition %. If the addition amount of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be exhibited. In some cases, smoothness and uniformity of the coating film may not be exhibited, have.

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

The colored photosensitive composition of the present invention may contain at least one of an organic carboxylic acid and an organic carboxylic acid anhydride for the purpose of improving developability or improving painting.

As the organic carboxylic acid, at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid can be mentioned.

Specific examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enantic acid, caprylic acid, glycolic acid, acrylic acid, But are not limited to, carboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Examples thereof include dicarboxylic acids such as tetramethylsuccinic acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarbalic acid, aconitic acid and camphoronic acid. Carboxylic acid and the like. Specific examples of the aromatic carboxylic acid include benzoic acid, toluic acid, cuminic acid, hemellitic acid, mesitylenic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, A carboxylic acid in which a carboxyl group is directly bonded to a phenyl group such as phenylacetic acid, hydro atropic acid, hydroquinic acid, mandelic acid, phenylsuccinic acid, atropathic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, , And a carboxylic acid in which a carboxyl group is bonded through a carbon bond from a phenyl group.

Among the organic carboxylic acids, monocarboxylic acids and dicarboxylic acids are preferable, and malonic acid, glutaric acid and glycolic acid are more preferable, and malonic acid is particularly preferable.

The molecular weight of the organic carboxylic acid is usually 1000 or less, and usually 50 or more. If the molecular weight of the organic carboxylic acid is too large, the effect of improving the drawing may be insufficient. If the molecular weight is too small, the amount of the organic carboxylic acid may decrease and the process may be contaminated by sublimation or volatilization.

Examples of the organic carboxylic acid anhydride include at least one of an aliphatic carboxylic acid anhydride and an aromatic carboxylic acid anhydride, and specific examples of the aliphatic carboxylic acid anhydride include acetic anhydride, trichloroacetic acid anhydride, trifluoroacetic acid anhydride, Anhydrous n-octadecylsuccinic acid, anhydrous 5-norbornene anhydride, maleic anhydride, maleic anhydride, maleic anhydride, anhydrous citric acid, anhydrous citraconic acid, anhydroglutaric acid, anhydrous 1,2-cyclohexene dicarboxylic acid, And an aliphatic carboxylic acid anhydride such as nhen-2,3-dicarboxylic acid. Specific examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and anhydrous naphthalic acid.

Among the organic carboxylic acid anhydrides, maleic anhydride, succinic anhydride, itaconic anhydride, and citraconic anhydride are preferable, and maleic anhydride is more preferable.

The molecular weight of the organic carboxylic acid 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 acid anhydride is too large, the effect of improving the drawing may be inadequate. If the molecular weight is too small, the amount of the organic carboxylic acid anhydride may decrease and the process may be contaminated by sublimation or volatilization.

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

The amount of the organic carboxylic acid and the organic carboxylic acid anhydride to be added is usually 0.01 wt% to 5 wt%, preferably 0.03 wt% to 3 wt%, based on the total solid content of the light-shielding photosensitive resin composition of the present invention % to be. If the addition amount is too small, a sufficient addition effect may not be obtained. If the addition amount is too large, surface smoothness and sensitivity may be deteriorated, and an un-dissolved and peeled off may occur.

[2-7-7] Thermal polymerization inhibitor

As the thermal polymerization inhibitor, for example, at least one of hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, .

The blending ratio of the thermal polymerization inhibitor is preferably in the range of 0 to 2% by weight based on the total solid content in the light-shielding photosensitive resin composition, and if it is more than that, the sensitivity of the photosensitive resin composition may be lowered.

[2-7-8] Plasticizer

Examples of the plasticizer include one or two kinds of plasticizers such as dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate and triacetyl glycerin. More than species are used.

The blending ratio of these plasticizers is preferably 5% by weight or less based on the total solid content in the light-shielding photosensitive resin composition, and if it is more than this, the curing point of the resin black matrix is lowered.

[3] Method for producing colored photosensitive composition

Next, a method for producing the colored photosensitive composition of the present invention will be described.

Hereinafter, the colored photosensitive composition using a pigment as a coloring agent will be described.

First, a pigment dispersion is prepared using (a) a pigment, (f) a dispersant and necessary components. Next, a colored photosensitive composition is prepared by mixing the pigment dispersion obtained above, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent. If necessary, the above-mentioned other components may be mixed.

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

As the method of producing the pigment dispersion according to the present invention, various methods can be adopted. An example is shown below.

First, a predetermined amount of pigment, solvent, and dispersant / dispersion auxiliary agent are each weighed, and in the dispersion treatment step, the pigment is dispersed to prepare a liquid pigment dispersion. As the pigment, solvent, and dispersant / dispersing aid, those described as constituent components of the above-mentioned colored photosensitive composition can be used.

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

Since the pigment is made into fine particles by carrying out the dispersion treatment, the color photosensitive composition using this pigment dispersion can improve the plate making performance such as coating properties and linearity.

When dispersing the pigment, the above-mentioned alkali-soluble resin or the like may be appropriately used in combination.

The temperature for the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. In addition, since the appropriate time varies depending on the composition of the pigment dispersion (pigment, solvent, dispersant / dispersion aid, etc.) and the size of the apparatus of the sand grinder, it is necessary to appropriately adjust the dispersion time.

The content of the pigment (a) in the pigment dispersion 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 dispersing agent (f) in the pigment dispersion is usually 5% by weight or more and 90% by weight or less, preferably 5% by weight or more and 60% by weight or less, and more preferably 5% by weight or more and 40% .

The content of the dispersion auxiliary agent in the pigment dispersion is usually 0.1 to 30% by weight, preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight based on the pigment.

The content of the alkali-soluble resin (b) in the pigment dispersion is usually from 0 to 100% by weight, preferably from 5 to 80% by weight, more preferably from 5 to 60% by weight, Or less.

[3-2] Production method of colored photosensitive composition

Next, the pigment dispersion (ink) obtained by the dispersion treatment and the other components required as the components of the colored photosensitive composition are added and stirred to obtain a uniform colored photosensitive composition solution. In this manufacturing process, since fine dust is often mixed in the liquid, it is preferable that the resulting colored photosensitive composition solution is subjected to filtration treatment with a filter or the like.

In addition, a colored photosensitive composition using a pigment (for example, a dye) as a coloring agent can be produced by a known method.

[4] Method of forming coloring spacer

The colored photosensitive composition of the present embodiment is used in the same manner as the known colored photosensitive composition for a color filter, but the case of being used as a colored spacer will be described below.

Typically, the colored photosensitive composition solution is supplied onto the substrate on which the colored spacer is to be formed, in a film or pattern form by a method such as coating, and the solvent is dried. Subsequently, pattern formation is carried out by photolithography in which exposure-development is performed. Thereafter, additional exposure or thermosetting treatment is carried out as necessary to form colored spacers on the substrate.

[4-1] Method of supplying to the substrate

The colored photosensitive composition of the present embodiment is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. The supplying method can be carried out by a conventionally known method, for example, a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, a spray coat method and the like. Among them, the die coating method is preferable from the viewpoint of comprehensive view that the amount of the coating liquid to be used is greatly reduced, there is no influence of mist or the like adhering to the spin coating method, and the generation of foreign matter is suppressed.

The coating amount varies depending on the application. For example, in the case of a colored spacer, the dry film thickness is usually in the range of 0.5 탆 to 10 탆, preferably 1 탆 to 9 탆, particularly preferably 1 탆 to 7 탆 to be. It is also important that the dry film thickness or the height of the finally formed coloring spacer is uniform over the entire area of the substrate. When the deviation is large, uneven defects are caused in the liquid crystal panel. It may also be supplied in the form of a pattern by an ink-jet method or a printing method.

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

[4-2] Drying method

Drying after supplying the colored photosensitive composition solution onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. It is also possible to combine the vacuum drying method in which the drying is performed in the decompression chamber without raising the temperature.

The drying conditions can be appropriately selected depending on the kind of the solvent component, the performance of the dryer to be used, and the like. The drying time is generally selected in the range of 40 to 130 占 폚 for 15 seconds to 5 minutes, preferably 50 to 110 占 폚, depending on the kind of the solvent component, the performance of the dryer to be used, In the range of 30 seconds to 3 minutes.

[4-3] Exposure method

Exposure is performed by overlapping a negative mask pattern on a coating film of the colored photosensitive composition and irradiating a light source of ultraviolet rays or visible light rays through the mask pattern. In the case of performing exposure using an exposure mask, there are a method of bringing the exposure mask close to the coating film of the colored photosensitive composition, a method of disposing the exposure mask at a position away from the coating film of the colored photosensitive composition, But may also be a method of projecting light. It is also possible to adopt a scanning exposure method using a laser beam not using a mask pattern. At this time, in order to prevent deterioration of the sensitivity of the photopolymerizable layer due to oxygen, if necessary, it may be performed in a deoxygenated atmosphere, or an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer, followed by exposure .

The light source used for the above exposure is not particularly limited. Examples of the light source include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, A laser light source such as an excimer laser, a nitrogen laser, a helium cardium laser, a blue violet semiconductor laser, and a near infrared semiconductor laser. An optical filter may be used when irradiating light of a specific wavelength.

The optical filter may be, for example, a thin film which can control the light transmittance at the exposure wavelength. In this case, for example, a Cr compound (oxide, nitride, oxynitride, fluoride or the like of Cr) Si, W, and Al.

In the method for collectively forming colored spacers different in height by photolithography, a light-shielding layer for blocking light transmission and an opening for transmitting light are provided as exposure masks, and the light transmittance of a part of the openings is different That is, a method of using an exposure mask having a light transmittance of 0% and a plurality of openings and having the highest average light transmittance (typically, a light transmittance of 100% (Intermediate transmissive opening) having a small average light transmittance with respect to an exposure mask (hereinafter referred to as an intermediate transmissive opening).

As the method of forming the intermediate transmission opening, it is preferable that the optical filter is arbitrarily disposed in the opening (transparent portion) of the mask pattern, that is, the opening portion (intermediate transmission opening portion) in which the optical filter is formed and the opening portion It is possible to adopt a method of using the arranged mask. This makes it possible to form a pattern having a different photopolymerization ratio according to the light transmittance of the opening portion by one exposure step, and it becomes possible to simultaneously form patterns having different heights at the same time, for example, in one exposure step.

As another method of forming the intermediate-transmission-opening portion, the light-shielding portion and the complete transmission portion described in JP-A-2003-344860 are arranged in a minute matrix pattern or a fine slit pattern so as to adjust the average light transmittance It is also possible to form an exposure mask having one intermediate penetration opening (the light transmittance to the fully transparent opening is small).

The exposure amount in the present embodiment is usually 1 mJ / cm2 or more, preferably 5 mJ / cm2 or more, more preferably 10 mJ / cm2 or more, usually 300 mJ / cm2 or less, preferably 200 mJ / cm 2 or less, and more preferably 150 mJ / cm 2 or less.

In the case of the proximity exposure method, the distance between the object to be exposed and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, usually 500 μm or less, preferably 400 Mu m or less, and more preferably 300 mu m or less.

[4-4] Development method

After the exposure described above, an image pattern can be formed on the substrate by developing using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, Mono-di- or triethanolamine, mono- or di- or trimethylamine, mono- or di- or triethylamine, mono- or di- or tri-alkylamine, or an inorganic or organic compound such as sodium dihydrogenphosphate, potassium dihydrogenphosphate or ammonium hydroxide, And organic alkaline compounds such as diisopropylamine, n-butylamine, mono- di- or triisopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline and the like. These alkaline compounds may be a mixture of two or more species.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters; Anionic surfactants such as alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfuric acid salts, alkylsulfonic acid salts and sulfosuccinic acid ester salts; and amphoteric surfactants such as alkyl betaines and amino acids.

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

The method of development processing is not particularly limited, but is usually carried out at a development temperature of from 10 캜 to 50 캜, preferably from 15 캜 to 45 캜, by a method such as immersion development, spray development, brush development or ultrasonic development do.

[4-5] Exposure and thermal curing treatment

The post-development substrate may be subjected to a post exposure or a heat curing treatment, if necessary, by the same method as the above-described exposure method. The heat curing treatment condition at this time is selected in the range of 100 占 폚 to 280 占 폚, preferably 150 占 폚 to 250 占 폚, and the time is selected in the range of 5 minutes to 60 minutes.

The colored photosensitive composition of the present embodiment is a colored photosensitive composition preferably used for forming a black matrix, an overcoat, a rib, a coloring spacer and the like in a color filter such as a liquid crystal display or the like. It is also possible to provide a colored photosensitive composition which is suitable for a method for simultaneously forming colored spacers having different heights, in particular by photolithography. According to the present embodiment, a high-quality color filter, a liquid crystal display, 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 circumferential spacer pattern.

The lower end face diameter of the colored spacer pattern of the fully transparent opening is usually more than 15 탆 and less than 45 탆, preferably more than 18 탆 and less than 40 탆. If it is lower than this range, compression characteristics tend to deteriorate, and if it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.

The lower end face diameter of the colored spacer pattern of the intermediate transmission opening is usually more than 20 μm but less than 50 μm, preferably more than 30 μm but less than 40 μm. If it is lower than this range, compression characteristics tend to deteriorate, and if it is higher than this range, the area on the substrate increases, which is not preferable on the panel structure.

The difference (? H) between the height of the colored spacer pattern of the fully transparent opening portion and the height of the colored spacer pattern of the intermediate transparent opening portion is usually 0.25 μm or more and 1.0 Mu] m or less, preferably 0.35 mu m or more and 0.80 mu m or less, and more preferably 0.4 mu m or more and 0.6 mu m or less. If it is lower than this range, the load resistance tends to deteriorate, and if it is higher than this range, it tends to exceed the compression limit.

[6] color filters

The color filter of the present invention has the above-described coloring spacer of the present invention as described above. For example, on the glass substrate as the transparent substrate, a black matrix, red, green, and blue pixel coloring layers, Forming a coloring spacer, and then forming an alignment film. As the orientation film, a resin film such as polyimide is preferable.

[7] liquid crystal display

The liquid crystal display of the present invention is provided with the color filter having the colored spacer of the present invention as described above. For example, the color filter and the liquid crystal driving side substrate described above are bonded to each other, . And injecting liquid crystal into the formed liquid crystal cell.

Example

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples unless they depart from the gist of the present invention.

The components of the colored photosensitive composition used in the following Examples and Comparative Examples are as follows.

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

<Alkali-soluble resin-1>

(Corresponding to MW = 3500 to 4500, acid value = about 110 mg-KOH / g, alkali soluble resin (A-2)) manufactured by Shin Nakamura Chemical Industries,

<Alkali-soluble resin-2>

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

<Alkali-soluble resin-3>

"SPCM-82" (MW = about 10000, acid value = about 24 mg-KOH / g, acrylate type alkali-soluble resin) manufactured by SHOWA POLYMER CO., LTD.

<Alkali-soluble resin-4>

In a 500 ml four-necked flask, 61.2 g of styrene / acrylic acid resin and John Krill 680 (BASF Japan) were uniformly dissolved in 138.6 g of propylene glycol monomethyl ether acetate at 80 占 폚. 0.24 g of tetraammonium chloride and 0.09 g of p-methoxyphenol were added and dissolved. Then, 71.4 g of propylene glycol monomethyl ether acetate and 34.4 g of 3,4-epoxycyclohexylmethyl acrylate (CYROMA A400, ) Was added dropwise over 40 minutes. The reaction solution was stirred at 80 DEG C for 32 hours 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 " (MW = about 8300, acid value = about 80 mg-KOH / g, acrylate-based alkali-soluble resin) manufactured by SHOWA POLYMER CO., LTD.

<Dispersant-1>

Quot; DisperBYK-2000 " (an A block having a quaternary ammonium salt group in the side chain and an acrylic A-B block copolymer composed of a B block having no quaternary ammonium salt group)

<Dispersant-2>

Quot; DisperBYK-LPN21116 " (an A block having a quaternary ammonium salt group and an amino group in a side chain and an acrylic AB block copolymer made of a B block having no quaternary ammonium salt group and an amino group in the side chain)

<Dispersant-3>

&Quot; DisperBYK-167 " (a urethane dispersant)

&Quot; S12000 "

Megapox F-475 manufactured by Dainippon Ink and Chemicals,

<Solvent-1>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-2>

MB: 3-methoxybutanol

<Solvent-3>

MBA: 3-methoxybutyl acetate

<Solvent-4>

CHN: Cyclohexanone

&Lt; Photopolymerization initiator >

A compound represented by the formula:

[Chemical Formula 16]

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

&Lt; Pigment dispersion - Preparation of 1 to 4 >

The pigment, dispersant, dispersing aid, alkali-soluble resin and propylene glycol monomethyl ether acetate (PGMEA) and methoxybutyl acetate (MBA) as solvents shown in Table 1 were mixed at the weight ratios shown in Table 1. Then, zirconia beads of 80% of the volume of the dispersion vessel were mixed, filled in a picomill dispersion vessel, and dispersed at necessary retention time to prepare respective pigment dispersions.

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

The pigment dispersions prepared in the above were mixed with the components shown in Table 2 in the ratios shown in Table 2 and stirred to prepare respective colored photosensitive composition coating liquids. Using the obtained colored photosensitive composition solution, a substantially cylindrical spacer pattern was formed by a method described later, and the shape, the step, the adhesion with the substrate, and the voltage holding ratio (VHR) were evaluated. The results are shown in Table 2.

[Method for collectively forming colored spacers having different heights]

The above photosensitive composition was coated on the ITO film of the glass substrate on which the ITO film was formed using a spinner. Subsequently, the coating film was formed by heating and drying at 110 DEG C for 70 seconds on a hot plate. The dried film thickness was 3.5 mu m.

The obtained coating film was subjected to exposure treatment using an exposure mask having a full-transmission opening portion of a circular pattern having a diameter of 15 mu m and an intermediate transmission opening portion having a circular pattern having a diameter of 35 mu m. The intermediate transmission opening is a thin film of Cr oxide with a light transmittance of 12.1% at 365 nm, a light transmittance of 16.5% at 405 nm, and a light transmittance of 19.6% at 436 nm. In addition, the light transmittance before and after the above three points is continuous and there is no inflection point. The exposure gap (distance between the mask and the coated surface) was 250 占 퐉.

Ultraviolet ray having a strength of 32 mW / cm < 2 > at 365 nm was used. The exposure dose was 50 mJ / cm 2. Ultraviolet irradiation was conducted under air. Subsequently, spraying was performed with a 0.1% potassium hydroxide aqueous solution at 25 캜 for 1.6 times the minimum developing time, and further rinsed with pure water. It is said that it does not melt even 120 seconds.

By these operations, a pattern in which unnecessary portions were removed was obtained. The substrate on which the pattern was formed was heated in an oven at 230 DEG C for 20 minutes to cure the pattern to obtain a roughly cylindrical spacer pattern.

[Shape Measurement of Colored Spacer Pattern]

The longitudinal cross-section of the colored spacer pattern passing through the center axis of the colored spacer pattern was profiled to measure the height of the colored spacer pattern and the cross-sectional diameters of the upper and lower bottom surfaces. For measurement, a three-dimensional non-contact surface shape measurement system MicromapMM3500-M100 manufactured by Ryoka, Ltd. was used.

Fig. 1 (A) and Fig. 1 (B) are views for explaining the shape of the substantially circular spacer pattern. 1 (A), the colored spacer pattern 1 is formed in a convex shape on a glass substrate 2, and has a substantially circular contour in plan view. 1 (B) is a cross-sectional view taken along the X-X line passing through the center axis 3 of the colored spacer pattern 1 of Fig. 1 (A). In Fig. 1 (B), the colored spacer pattern 1 has a roughly rectangular outline. This outline is defined as the profile 4 of the colored spacer pattern 1 and the intersection of the pattern side surface portion 41 of the profile 4 and the glass substrate 2 is defined as intersection A and A '. The distance from the surface of the glass substrate 2 to the point at the highest position of the profile 4 is the pattern height H and the distance between the intersection point A and the point A '

[Evaluation of step difference]

(? H) between the height of the colored spacer pattern of the fully transparent opening portion and the height of the colored spacer pattern of the intermediate transparent opening portion was more than 0.35 占 퐉 and 0.8 占 퐉 or less was evaluated as?, 0.25 占 퐉 or more and 0.4 占 퐉 or less? . The results are shown in Table 2.

[Evaluation of adhesion]

As described above, when the sizes of the intermediate transmission opening portions are 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 30, 35, 40 , 45, and 50 mu m, and 24 patterns having different sizes were formed. The size (diameter) of the smallest intermediate permeation opening portion in which none of the 24 patterns was lost was measured. A sample having a size of 15 mu m or less was evaluated as & cir & The results are shown in Table 2.

[Evaluation of voltage holding ratio (VHR)] [

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

&Lt; Production of liquid crystal cell &

An extraction electrode having a width of 2 mm was connected to the central portion of one side of the electrode substrate A (ITO BETA for evaluation manufactured and manufactured) and the copper glass substrate having a width of 2.5 cm on the ITO film An electrode substrate B (ITO SZ-B111MIN (B) for evaluation and fabrication, evaluation) having an ITO film of 1 cm square was prepared.

Each colored photosensitive composition solution was coated on the electrode substrate A, vacuum-dried for 1 minute, and then baked on a hot plate at 110 DEG C for 70 seconds to obtain a coated film having a dried film thickness of 3.5 mu m. Thereafter, the outer edge portion was masked by 2 mm, and image exposure was performed under exposure conditions of 50 mJ / cm 2 using a 3 kW high-pressure mercury lamp, respectively. Subsequently, a shower phenomenon at a water pressure of 0.15 MPa at 25 캜 was performed using an aqueous solution of about 0.1 wt% of potassium hydroxide at 25 캜, development was stopped with pure water, and rinsed with a water spray. The shower developing time was adjusted within a range of 10 to 120 seconds to be about 1.6 times as long as the time when the photosensitive layer was dissolved and removed (break time). It is said that it does not melt even 120 seconds.

The thus-formed electrode substrate was post-baked at 230 DEG C for 20 minutes to obtain an electrode substrate on which a resist was formed (resist substrate). Thereafter, the polyimide solution was coated on the resist substrate, pre-baked on a hot plate at 70 DEG C for 2 minutes, and post-baked at 220 DEG C for 24 minutes. The resist substrate thus obtained was cut into a substrate having a length of 2.5 cm and a length of 2.5 cm to complete an electrode substrate A for evaluation.

On the other hand, a polyimide solution was applied also on the electrode substrate B, prebaked on a hot plate at 70 占 폚 for 2 minutes, and post-baked at 220 占 폚 for 24 minutes to complete an electrode substrate for evaluation B.

Thereafter, an epoxy resin sealant containing silica beads having a diameter of 5 占 퐉 was applied to the outer periphery of the electrode substrate B using a dispenser, and then the electrode substrate A was placed on the surface (sealing side) of the electrode substrate B, The coated surface was attached with squeezing to complete an empty cell. And heated at 180 캜 for 2 hours in a hot air circulation furnace.

A liquid crystal (MLC-6608, manufactured by Merck Japan Co., Ltd.) was injected into the empty cell thus obtained and the periphery was sealed with a UV curable sealant to complete a liquid crystal cell for measuring the voltage holding ratio.

&Lt; Evaluation of voltage holding ratio (VHR) >

The liquid crystal cell was subjected to annealing (heating at 105 DEG C for 2.5 hours in a hot air circulation furnace) and then applied to the evaluation electrode substrates A and B under the conditions of a voltage of 5 V, 0.6 Hz and a frame time of 1667 msec. Was measured by "VHR-6254 type" manufactured by TOYO TECHNICAL CO., LTD.

From the results shown in Table 2, it is possible to obtain a colored spacer excellent in the formation of the shape of the completely transparent opening portion and the intermediate transparent opening pattern, the control of the level difference, the good adhesion and the excellent voltage retention rate of the liquid crystal And the coloring spacers having different heights are collectively formed.

While the invention has been described in detail and with reference to specific embodiments thereof, it is evident to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. This application is based on Japanese patent application (patent application 2011-233900) filed on October 25, 2011, the content of which is incorporated herein by reference.

Industrial availability

The colored photosensitive composition of the present invention is a colored photosensitive composition preferably used for forming colored spacers or the like in a color filter such as a liquid crystal display, and particularly when a coloring spacer having different heights is collectively formed by photolithography , Formation of a shape, step difference, adhesion, and electric reliability of a liquid crystal are excellent. The present invention can provide a high quality color filter, a liquid crystal display device, and the like.

Claims

(a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, As a colored photosensitive composition used for collectively forming spacers,
(b) an alkali-soluble resin containing at least one of the following alkali-soluble resin (A-1) and alkali-soluble resin (A-2)
(f) an acrylic block copolymer containing a nitrogen atom as a dispersant,
(d) the weight ratio of the (b) alkali-soluble resin to the ethylenically unsaturated compound is 2 or more and less than 7,
The total amount of the alkali-soluble resin (A-1) and the alkali-soluble resin (A-2) relative to the total solid content in the colored photosensitive composition is 12% by weight or more.
&Lt; Alkali-soluble resin (A-1) >
A resin obtained by adding an?,? - unsaturated monocarboxylic acid or an?,? - unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety to the epoxy resin and further reacting the polybasic acid anhydride
&Lt; Alkali-soluble resin (A-2) >
Unsaturated monocarboxylic acid or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety is added to the epoxy resin, and further, a polyhydric alcohol and a polybasic acid anhydride are reacted

The method according to claim 1,
The total amount 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.

The colored photosensitive composition according to claim 1, wherein the total ratio 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 wt% or more and 60 wt% or less.

The method according to claim 1,
(a) the content of the colorant is less than 30% by weight based on the total solid content in the colored photosensitive composition.

The method according to claim 1,
(a) the content of the coloring agent is 25% by weight or more based on the total solid content in the colored photosensitive composition.

The method according to claim 1,
A colored photosensitive composition comprising (a) at least one of the following (1) red pigment and (2) a blue pigment and the following (3) purple pigment as the colorant:
(1) Red pigment selected from CI Pigment Red 177, 254
(2) CI Pigment Blue 15: 6 blue pigment
(3) CI Pigment Violet 23 purple pigment

The method according to claim 1,
(a) a coloring photosensitive composition comprising, as a colorant, CI Pigment Red 254 and CI Pigment Blue 15: 6.

The method according to claim 1,
(f) at least one of an A block having at least one of a quaternary ammonium group and an amino group in a side chain and an AB block copolymer and a BAB block copolymer comprising a quaternary ammonium salt group and a B block having no amino group By weight.

The method according to claim 1,
(f) a block copolymer comprising at least one of an A block having a quaternary ammonium group and an amino group in a side chain and an AB block copolymer and a BAB block copolymer having a quaternary ammonium salt group and an amino group, Lt; / RTI >

The method according to claim 1,
(f) at least one of an AB block copolymer and a BAB block copolymer composed of an A block having an amino group and no quaternary ammonium salt group in the side chain and a B block having no quaternary ammonium salt group and no amino group Lt; / RTI >

The method according to claim 1,
(c) a photo-sensitive composition containing an oxime ester compound as a photo polymerization initiator.

A colored spacer having different heights collectively formed by the colored photosensitive composition according to any one of claims 1 to 11.

A color filter comprising the coloring spacer according to claim 12.

A liquid crystal display device comprising the color filter according to claim 13.

A method for collectively forming colored spacers having different heights by photolithography using the colored photosensitive composition according to any one of claims 1 to 11.