JP5124341B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a photosensitive coloring composition used for the production thereof.

  In recent years, liquid crystal display devices have been applied to television monitor applications, personal computer monitor applications, mobile applications, and the like, and pigment dispersion type color filters are widely used as color filters. The pigment-dispersed color filter was sensitized by adding a photopolymerizable monomer and a polymerization initiator to a colored composition obtained by dispersing a pigment in a resin (such as an acrylic resin) using a dispersant, a solvent, or the like. A photolithographic method is widely used in which a photosensitive coloring composition is applied on a transparent support such as a glass substrate to form a colored coating film such as a colored layer or a light shielding layer, and is patterned. Further, the patterned coating film is post-baked at a high temperature of 200 ° C. or higher in order to impart resistance in the subsequent steps.

  In addition, the general use of liquid crystal display devices has progressed, and a significant reduction in product price is expected. Accordingly, cost reduction of color filters has become a problem in recent years. Recycle and reuse glass substrates after post-baking that have recently failed (hereinafter referred to as “rework”), eliminating waste of glass substrates that account for the largest percentage of the material cost of color filters. Attempts have been made as one of effective and simple means for reducing costs. (Hereinafter, the ability to rework efficiently will be described as “reworkability is good.”)

  As a means for reworking, there is a method in which a colored coating film patterned as a color filter after post-baking is peeled off from a glass substrate using a reworking liquid, and is again in a state before applying a photosensitive coloring composition to the glass substrate. is there. The coating film on the glass substrate after post-baking has high heat resistance and solvent resistance, and in order to rework, a high-temperature, high-concentration strong alkaline solution must generally be used as the rework liquid. In order to prevent clogging of the rework liquid that is circulated through the filter that collects peeled pieces, not only the colored coating film of the post-baked color filter that has been patterned during rework is peeled off from the glass substrate, but also peeled off. There is a demand for making the pieces finer.

  Patent Document 1 discloses a photosensitive coloring composition using a resin containing a carboxyl group in a resin and not having a hydroxyl group in the resin. By using the resin, the above-described reworkability is improved. However, the photosensitive coloring composition has low dispersion stability and insufficient long-term storage stability.

Patent Document 2 discloses a photosensitive coloring composition using a resin having an alkylene group in which a benzene ring is substituted at a side chain or a terminal in order to enhance long-term storage stability of the photosensitive coloring composition. This composition has good adsorption / orientation on the pigment surface due to the effect of π electrons on the benzene ring, and exhibits excellent dispersibility. However, when the post-baking after the patterning of the photosensitive coloring composition using the resin, due to the influence of the thermosetting reaction, the coating film of the color filter after the patterning post-baking does not peel in the first place, Even if it does, since a peeling piece will become a big lump and will exist in rework liquid, it will cause clogging of a circulation filter, and it will become a rework defect.
Japanese Patent Laid-Open No. 10-171119 JP 2004-101728 A

  Even in the case of a photosensitive coloring composition obtained by mixing a resin having good reworkability but poor dispersion stability and a resin having good dispersion stability but poor reworkability, the reworkability is not sufficient.

  The present invention relates to a photosensitive coloring composition that is compatible with reworkability and long-term storage stability and does not impair basic performance such as developability, and a filter segment and / or black matrix formed using the same. An object is to provide a color filter provided.

  The subject is a photosensitive coloring composition comprising a resin, a dye, a photopolymerization initiator, a polymerizable monomer, and a solvent, and the resin is represented by the following general formula (1). A photosensitive coloring composition comprising a structural unit (a), a structural unit (b) having a carboxyl group, and a structural unit (c) having no other hydroxyl group It is solved by.

  General formula (1):

(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ may have a hydrogen atom or a benzene ring. It is a good alkyl group having 1 to 20 carbon atoms, and l is an integer of 1 to 15.)
Moreover, in the preferable aspect of the photosensitive coloring composition by this invention, the said structural unit (b) is following General formula (2):

(In General Formula (2), R ⁴ is a hydrogen atom or a methyl group, and X ¹ is General Formula (3):

[In General Formula (3), R ⁵ is an alkylene group having 2 to 12 carbon atoms, and m is an integer of 1 or 2. ]
Y ¹ is a group represented by the general formula (4):

[In General Formula (4), R ⁶ is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 6 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, and n is 0 or 1 It is an integer. ]
It is group represented by these. )
The structural unit (b1) and / or the following general formula (5):

(In the general formula (5), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a glycidyl group, a methyl glycidyl group, a 3,2-glycidoxyethyl group, a 3,4-epoxycyclohexyl group, 3 , 4-epoxybutyl group or 4,5-epoxypentyl group.)
A photosensitive coloring composition characterized in that it is a structural unit (b2) obtained by adding an unsaturated monobasic acid to the structural unit (d) represented by formula (I) and adding a polybasic acid anhydride to the generated hydroxyl group. It is a thing.

  Moreover, in the preferable aspect of the photosensitive coloring composition by this invention, the said resin is the precursor (a ') 1-35 weight% of a structural unit (a), and the precursor (b') of a structural unit (b). The photosensitive coloring composition is a resin obtained by copolymerizing 10 to 90% by weight and 1 to 75% by weight of the precursor (c ′) of the structural unit (c).

  Moreover, in the preferable aspect of the photosensitive coloring composition by this invention, when the said resin copolymerizes a principal chain, the precursor (a ') 1-35 weight% of a structural unit (a), a structural unit (d Unsaturated monobasic acid is added to a resin obtained by copolymerizing 4 to 75% by weight of the precursor (d ′) of 1) and 1 to 75% by weight of the precursor (c ′) of the structural unit (c). After that, the photosensitive coloring composition is a resin obtained by adding a polybasic acid anhydride to the generated hydroxyl group.

  In a preferred embodiment of the photosensitive coloring composition according to the present invention, the precursor (a ′) of the structural unit (a) contains paracumylphenol ethylene oxide or propylene oxide modified (meth) acrylate. It is the photosensitive coloring composition characterized by these.

  In a preferred embodiment of the photosensitive coloring composition according to the present invention, the precursor (c ′) of the structural unit (c) contains (meth) acrylic acid alkyl ester. It is a composition.

  In a preferred embodiment of the photosensitive coloring composition according to the present invention, the precursor (c ′) of the structural unit (c) is benzyl (meth) acrylate and / or dicyclopentanyl (meth) acrylate and / or A photosensitive coloring composition containing dicyclopentenyl (meth) acrylate and / or cyclopentanyloxyethyl (meth) acrylate.

  Furthermore, the present invention relates to a color filter comprising a filter segment and / or a black matrix formed from the photosensitive coloring composition according to the present invention.

  By using the photosensitive coloring composition with good reworkability of the present invention, it is possible to eliminate the waste of the glass substrate in the production of the color filter and obtain a low-cost color filter.

<Resin>
First, the resin contained in the photosensitive coloring composition of the present invention will be described.

In addition, when expressed as “(meth) acrylic acid”, “(meth) acrylate”, and “(meth) acryloyloxy”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, respectively. And “acryloyloxy and / or methacryloyloxy”.
The resin contained in the photosensitive coloring composition of the present invention includes a structural unit (a) represented by the following general formula (1), a structural unit (b) having a carboxyl group, and other structural units having no hydroxyl group ( It is a vinyl polymer composed of c). The structural unit (a) functions as a solvent affinity site, and the structural unit (b) functions as a pigment adsorptive site and an alkali-soluble site.

  General formula (1):

(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ may have a hydrogen atom or a benzene ring. It is a good alkyl group having 1 to 20 carbon atoms, and l is an integer of 1 to 15.)
In the present invention, a resin satisfying the following characteristics is used.
(1) Dispersibility It is possible to prevent aggregation of the pigment in the coloring composition and maintain a finely dispersed state for a long period of time.
(2) Developability Only the unexposed areas can be removed with an (alkaline) developer during development.
(3) Reworkability The colored coating film after post-baking can be removed with a (strong alkaline) reworking solution, and the peeled piece of the colored coating film does not become coarse.

In order to satisfy all of these characteristics, the structural unit (a), the structural unit (b), and the structural unit (c) are allowed to coexist in a well-balanced manner, maintain dispersion stability, and are unexposed during development. (Alkaline) developer penetrates only the part, swells only the unexposed part, reacts with the carboxyl group of the unexposed part, partially solubilizes and removes it, and at the time of rework (exits high alkalinity) to the exposed part It is important to design the resin so that the rework liquid penetrates, swells the exposed area, reacts with the carboxyl group, and is partially solubilized and removed.
Moreover, it is also possible to design in consideration of the balance of the structural unit (a), the structural unit (b), and the structural unit (c) so that the removed coating film flows out into the developer and the rework liquid as finely as possible. Important for production efficiency.

  The resin contained in the photosensitive coloring composition of the present invention includes a precursor (a ′) of a structural unit (a) represented by the following general formula (1) and a precursor of a structural unit (b) having a carboxyl group ( It is obtained by copolymerizing b ′) and other precursor (c ′) of the structural unit (c) having no hydroxyl group.

  The structural unit (a) represented by the following general formula (1) will be described.

  In the structural unit (a), the π electron of the side chain benzene ring and the alkylene portion of the side chain having an appropriate length effectively function as a solvent affinity site. Since the side chain benzene ring is oriented to the pigment, it promotes resin adsorption to the pigment and also has a function of suppressing aggregation of the pigment. Therefore, the dispersion of the pigment surface-treated with the resin having the structural unit (a) can maintain high storage stability.

  In addition, when the structural unit (b) having a carboxyl group functioning as a pigment surface adsorption site at the time of pigment dispersion reacts with an alkali at the time of development or rework to become an alkali-soluble site, the structural unit (a) Since it functions as a good hydrophobic part for the soluble part, the part to be removed can be finely and efficiently removed.

  General formula (1):

(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ may have a hydrogen atom or a benzene ring. It is a good alkyl group having 1 to 20 carbon atoms, and l is an integer of 1 to 15.)

In general formula (1), the alkyl group of R ³ has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R ³ is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment, but when the carbon number exceeds 10, The steric hindrance effect becomes high and shows a tendency to prevent even the adsorption / orientation of the benzene ring to the pigment. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ³ becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely reduced. Examples of the alkyl group having a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group. By increasing one side chain benzene ring, solvent affinity and pigment orientation are further improved, and not only dispersibility but also developability and reworkability are improved.

  As the precursor (a ′) of the structural unit (a), phenol ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, nonylphenol EO modified ( And (meth) acrylate, nonylphenol PO-modified (meth) acrylate, and the like. The precursor (a ′) is not limited to the above examples, and may be used alone or in combination of two or more. Among the precursors (a ′), EO or PO-modified (meth) acrylate of paracumylphenol adds not only the π-electron effect of the benzene ring, but also its steric effect, and better adsorption to the pigment. / It is most preferable because an orientation plane can be formed.

  Next, the structural unit (b) will be described.

  The structural unit (b) having a carboxyl group functions as a pigment adsorbing group during dispersion, as an alkali-soluble group in an unexposed portion during development, and as a strong alkali-soluble group in an exposed portion during rework.

  As the precursor (b ′) of the structural unit (b) having a carboxyl group, an unsaturated dicarboxylic acid such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, maleic acid, maleic anhydride, fumaric acid, or The compound etc. which contain carboxyl groups, such as the anhydride, and have an ethylenically unsaturated double bond are mentioned.

  The structural unit (b) having a carboxyl group is particularly preferably a structural unit (b1) represented by the general formula (2) and / or a structural unit (d) represented by the following general formula (5). It is a structural unit (b2) obtained by adding an unsaturated monobasic acid and adding a polybasic acid anhydride to the generated hydroxyl group. The structural unit (b1) is obtained by copolymerizing the precursor (b1 ′) with another precursor, and the structural unit (d) is copolymerized with the precursor (d ′) with another precursor. It is obtained by doing.

 General formula (2):

(In General Formula (2), R ⁴ is a hydrogen atom or a methyl group, and X ¹ is General Formula (3):

[In General Formula (3), R ⁵ is an alkylene group having 2 to 12 carbon atoms, and m is an integer of 1 or 2. ]
Y ¹ is a group represented by the general formula (4):

[In General Formula (4), R ⁶ is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 6 to 8 carbon atoms, or an arylene group having 6 to 14 carbon atoms, and n is 0 or 1 It is an integer. ]
It is group represented by these. )
General formula (5):

(In the general formula (5), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a glycidyl group, a methyl glycidyl group, a 3,2-glycidoxyethyl group, a 3,4-epoxycyclohexyl group, 3 , 4-epoxybutyl group or 4,5-epoxypentyl group.)

In the general formula (3), as a specific example of R ⁵ , as an alkylene group having 2 to 12 carbon atoms, for example, —CH ₂ —CH ₂ —, —CH ₂ —CH (CH ₃ ) —, —CH (CH _{3) -CH 2 -, - (} CH 2) 5 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, - CH 2 -CH 2 -C (CH _{3) 2 -, - CH (} CH 3) -CH 2 -CH 2 -, - CH (CH 2 CH 3) -CH 2 -CH 2 -, - CH (CH 2 CH 2 CH 3) -CH 2 -CH _{2 -, - CH (CH 3} ) -CH 2 -CH 2 -CH 2 -, - CH (CH 2 CH 3) -CH 2 -CH 2 -CH 2 -, - CH (CH 2 CH 2 CH 3) - CH ₂ —CH ₂ —CH ₂ —, —CH [(CH ₂ ) ₅ CH ₃ ] — (CH ₂ ) ₁₀ — and the like can be mentioned.

In the general formula (4), specific examples of R ^6, the alkylene group having 2 to 20 carbon atoms, _{e.g., -CH 2 -CH 2 -, -} CH 2 -CH 2 -CH 2 -, - CH 2 - _{CH (CH 3) -, -} CH (CH 3) -CH 2 -, - CH 2 -CH 2 -CH 2 -CH 2 -, - CH 2 -CH 2 -CH (CH 3) -, - CH 2 - CH [(CH _{2) 3} CH _3] -, - CH ₂ -CH [(CH _{2) 7} CH _3] -, - CH ₂ -CH [(CH _{2) 9} CH _3] -, - CH ₂ -CH [ (CH _{2) 11} CH _3] -, - CH ₂ -CH [(CH _{2) 13} CH _3] -, - CH ₂ -CH [(CH _{2) 15} CH _3] -, and -CH ₂ -CH [( CH _{2) 17} CH _3] -, and the like,
Examples of the cycloalkylene group having 6 to 8 carbon atoms include cycloalkylene groups represented by the following general formulas (6) to (9),
Examples of the arylene group having 6 to 14 carbon atoms include arylene groups represented by the following general formulas (10) to (13).

In general formula (4), examples of R ⁶ include those having a substituent on the alkylene group, cycloalkylene group, and arylene group.
General formula (6):

General formula (7):

General formula (8):

General formula (9):

General formula (10):

General formula (11):

Formula (12):

General formula (13):

In general formula (4), examples of R ⁶ include those having a substituent on the alkylene group, cycloalkylene group, and arylene group.

From the viewpoint of the balance between developability and reworkability, the acrylic acid dimer [R ⁵ : —CH ₂ —CH ₂ —], β is preferred as the precursor (b1 ′) of the structural unit (b1) having a carboxyl group. - carboxyethyl (meth) acrylate [R ^5: -CH ₂ -CH ₂ -], 2- (meth) acryloyloxyethyl succinate _{^{[R 5: -CH 2 -CH 2 -}} , R 6: -CH 2 -CH ₂ -], 2- (meth) acryloyloxyethyl phthalate _{^{[R 5: -CH 2 -CH 2 -}} , R 6: a phenylene group], 2- (meth) acryloyloxyethyl hexahydrophthalic acid [R ^5: - ^{_{CH 2 -CH 2 -, R 6}} : cyclohexylene], 2- (meth) acryloyloxy propyl acid _{^{[R 5: -CH 2 -CH (CH}} 3) -, R 6: -CH 2 -CH 2 - ], 2- (meth) acryl Acryloyloxy propyl phthalate _{^{[R 5: -CH 2 -CH (CH}} 3) -, R 6: a phenylene group], 2- (meth) acryloyloxyethyl hexahydrophthalic acid [R ^5: -CH ₂ -CH (CH ₃ )-, R ⁶ : cyclohexylene group], polyethylene oxide modified succinic acid (meth) acrylate [R ⁵ : —CH ₂ —CH ₂ —, R ⁶ : —CH ₂ —CH ₂ —], ω-carboxy-poly Caprolactone-modified mono (meth) acrylate [R ⁵ : — (CH ₂ ) ₅ —], polyethylene oxide modified phthalic acid (meth) acrylate [R ⁵ : —CH ₂ —CH ₂ —, R ⁶ : phenylene group] and the like. Can be mentioned. The precursor (b ′) is not limited to the above examples, and may be used alone or in combination of two or more.

  The structural unit (b2) may be obtained by copolymerizing a precursor (b ′) obtained by adding an unsaturated monobasic acid to the precursor (d ′) and adding a polybasic acid anhydride to the generated hydroxyl group. Alternatively, the precursor (d ′) is polymerized to form the structural unit (d), an unsaturated monobasic acid is added, and a polybasic acid anhydride is added to the generated hydroxyl group.

  As the precursor (d ′) of the structural unit (d) represented by the general formula (5), glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3, 4 epoxy butyl (meth) acrylate and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Moreover, as an unsaturated monobasic acid added to the structural unit (d) represented by the general formula (5), (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, (meta ) Monocarboxylic acids such as α-position haloalkyl, alkoxyl, halogen, nitro, and cyano substituents of acrylic acid, and the like may be used alone or in combination of two or more.

  Furthermore, examples of the polybasic acid anhydride to be reacted with the hydroxyl group of the addition reaction product include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. Alternatively, two or more types may be used in combination.

  If necessary, a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride is used, such as increasing the number of carboxyl groups in the structural unit (b ′). Can be used to hydrolyze the remaining anhydride groups.

  The carboxyl group of the structural unit (b1) and / or the structural unit (b2) is farther from the main chain and has less steric hindrance than the carboxyl group of the structural unit polymerized from a precursor such as (meth) acrylic acid. Therefore, the rework liquid (strong alkaline aqueous solution) penetrates quickly into the coating film whose crosslink density is increased by exposure, and the compatibility is good, so that swelling, reaction, and dissolution proceed smoothly.

  As the precursor (c ′) of the structural unit (c) having no hydroxyl group, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate, (Iso) pentyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl Examples include (meth) acrylic acid esters such as (meth) acrylate. The precursor (c ′) is not limited to the above examples, and may be used alone or in combination of two or more.

  The reason why the structural unit (c) is limited to “has no hydroxyl group” is that when the hydroxyl group is contained in the resin, the carboxyl group of the structural unit (b) is obtained by heat treatment of the coating film. This is because a dehydration condensation reaction occurs, and as a result, the crosslink density of the ester bond increases and the reworkability deteriorates.

  The structural unit (c) is a structural unit necessary for obtaining physical properties as a colored coating film that cannot be achieved only by the structural unit (a) and the structural unit (b). From the viewpoint of film forming property, the precursor (c ′) is preferably an alkyl (meth) acrylate, and from the viewpoint of pigment dispersibility, stability, and coating film resistance, benzyl (meth) acrylate and / or dicyclopenta. More preferred are nyl (meth) acrylate and / or dicyclopentenyl (meth) acrylate and / or dicyclopentanyloxyethyl (meth) acrylate.

  When copolymerizing the precursor (a ′), the precursor (b ′), and the precursor (c ′) in order to obtain a resin contained in the photosensitive coloring composition of the present invention, The polymerization ratio of the precursor (a ′) is preferably 1 to 50% by weight, and more preferably 1 to 35% by weight. When the polymerization ratio of the precursor (a ′) is less than 1% by weight, the pigment dispersion effect is lowered and a sufficient dispersion effect cannot be obtained. On the other hand, if it exceeds 50% by weight, the hydrophobicity increases, the compatibility with other components in the photosensitive coloring composition is significantly reduced, the developability of the photosensitive coloring composition is reduced, the generation of residues, Precipitation of monomers and photoinitiators may occur. The resin having the structural unit (a) of the resin obtained by copolymerizing 1 to 35% by weight of the precursor (a ′) has a proportion of the structural unit (a) of the structural unit (b) and the structural unit (c). ) And good developability and reworkability are exhibited.

  When copolymerizing the precursor (a ′), the precursor (b ′), and the precursor (c ′) in order to obtain a resin contained in the photosensitive coloring composition of the present invention, The polymerization ratio of the precursor (b ′) is preferably 5 to 91% by weight, and more preferably 10 to 90% by weight. When the proportion of the precursor (b ′) is less than 5% by weight, sufficient reactivity with the developer or the rework solution cannot be obtained. On the other hand, when the amount is more than 91% by weight, the amount of carboxyl groups in the photosensitive composition increases, structural viscosity due to hydrogen bonding occurs, and dispersion stability may decrease. The resin having the structural unit (b) obtained by copolymerizing 10 to 90% by weight of the precursor (b ′) has a proportion of the structural unit (b) of the structural unit (a) and the structural unit (c). Balance is good, and excellent developability and reworkability are exhibited.

  When copolymerizing the precursor (a ′), the precursor (b ′), and the precursor (c ′) in order to obtain a resin contained in the photosensitive coloring composition of the present invention, The polymerization ratio of the precursor (c ′) is preferably 1 to 80% by weight, and more preferably 1 to 75% by weight. If the proportion of the precursor (c ′) is less than 1% by weight, sufficient film properties cannot be obtained. On the other hand, when the amount is more than 80% by weight, the structural unit (a) and the structural unit (b) are decreased, and sufficient dispersibility, developability and reworkability cannot be obtained. The resin having the structural unit (c) obtained by copolymerizing 1 to 75% by weight of the structural unit (c) has a proportion of the structural unit (a) of the structural unit (a) and the structural unit (b). Good balance and excellent developability and reworkability.

  When copolymerizing the precursor (a ′), the precursor (d ′), and the precursor (c ′) in order to obtain a resin contained in the photosensitive coloring composition of the present invention, The polymerization ratio of the precursor (a ′) is preferably 1 to 50% by weight, and more preferably 1 to 35% by weight. When the polymerization ratio of the precursor (a ′) is less than 1% by weight, the pigment dispersion effect is lowered and a sufficient dispersion effect cannot be obtained. On the other hand, if it exceeds 50% by weight, the hydrophobicity increases, the compatibility with other components in the photosensitive coloring composition is significantly reduced, the developability of the photosensitive coloring composition is reduced, the generation of residues, Precipitation of monomers and photoinitiators may occur. Resin obtained by adding unsaturated monobasic acid and polybasic acid anhydride to resin having structural unit (a) of resin obtained by copolymerizing 1 to 35% by weight of precursor (a ′) Has a good balance between the structural unit (a) and the structural unit (b2) and the structural unit (c), and exhibits excellent developability and reworkability.

  When copolymerizing the precursor (a ′), the precursor (d ′), and the precursor (c ′) in order to obtain a resin contained in the photosensitive coloring composition of the present invention, The polymerization ratio of the precursor (d ′) is preferably 2 to 80% by weight, and more preferably 4 to 75% by weight. When the proportion of the precursor (d ′) is less than 2% by weight, the copolymer of the present invention in which an unsaturated monobasic acid is added to the copolymer and a polybasic acid anhydride is added to the generated hydroxyl group. A sufficient effect cannot be obtained. On the other hand, when the amount is more than 80% by weight, the amount of carboxyl groups in the photosensitive composition increases, structural viscosity due to hydrogen bonding occurs, and dispersion stability may decrease. A structural unit obtained by adding an unsaturated monobasic acid and a polybasic acid anhydride to a resin having a structural unit (d) obtained by copolymerizing 4 to 75% by weight of the precursor (d ′) ( In the resin having b2), the proportion of the structural unit (b2) is well balanced between the structural unit (a) and the structural unit (c), and excellent developability and reworkability are exhibited.

When copolymerizing the precursor (a ′), the precursor (d ′), and the precursor (c ′) in order to obtain a resin contained in the photosensitive coloring composition of the present invention, The polymerization ratio of the precursor (c ′) is preferably 1 to 80% by weight, and more preferably 1 to 75% by weight. If the proportion of the precursor (c ′) is less than 1% by weight, sufficient film properties cannot be obtained. On the other hand, when the amount is more than 80% by weight, the structural unit (a) and the structural unit (b2) are decreased, and sufficient dispersibility, developability, and reworkability cannot be obtained. Resin obtained by adding unsaturated monobasic acid and polybasic acid anhydride to resin having structural unit (c) of resin obtained by copolymerizing 1 to 75% by weight of precursor (c ′) Has a good balance between the structural unit (c) and the structural unit (a) and the structural unit (b2), and exhibits excellent developability and reworkability. Pigment dispersibility, stability, and coating film resistance From the viewpoint of the above, as the precursor (c ′) of the structural unit (c), preferred benzyl (meth) acrylate and / or dicyclopentanyl (meth) acrylate and / or dicyclopentenyl (meth) acrylate and / or cyclopenta The weight ratio of nyloxyethyl (meth) acrylate is preferably 1 to 80% by weight in all precursors (including unsaturated monobasic acid and polybasic acid anhydride when formed from the structural unit (d)). When it is less than 1% by weight, the physical properties of the coating film are not sufficient, and when it is more than 80% by weight, the dispersibility of the pigment, the developability, and the reworkability are poor because the structural unit (a) and the structural unit (b) are small.

  The resin contained in the photosensitive coloring composition of the present invention comprises a precursor (a ′), a precursor (b ′), and a precursor (c ′) in an inert gas in the presence of a radical polymerization initiator. Radical polymerization is performed at 50 to 150 ° C. for 2 to 10 hours under an air flow, or the precursor (a ′), the precursor (d ′), and the precursor (c ′) are present in the presence of a radical polymerization initiator. In an inert gas stream, radical polymerization is performed at 50 to 150 ° C. over 2 to 10 hours, and then air substitution is performed and hydroquinone is added to react the unsaturated monobasic acid at 50 to 150 ° C. over 2 to 10 hours. It can be obtained by adding triethylamine and reacting the polybasic acid anhydride at 50 to 150 ° C. for 2 to 10 hours. This polymerization reaction can be performed in the presence of a solvent, if necessary.

  Examples of radical polymerization initiators include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, t-butyl peroxybenzoate, Examples include azo compounds such as 2′-azobisisobutyronitrile, but are not limited thereto, and these may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in a proportion of 1 to 20 parts by weight with respect to 100 parts by weight of the total resin precursor (total of precursor (a), precursor (b) and precursor (c)). Is done.

  Solvents that can be used during the radical polymerization reaction include water and / or water-miscible organic solvents, or acetates such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate; ketones such as cyclohexanone and methyl isobutyl ketone; xylene, Ethylbenzene or the like can be used. Examples of the water-miscible organic solvent include alcohol solvents such as ethyl alcohol, isopropyl alcohol and n-propyl alcohol, and mono- or dialkyl ethers of ethylene glycol or diethylene glycol, but are not limited thereto. It may be used alone or in combination of two or more.

  The weight average molecular weight (Mw) of the resin contained in the photosensitive coloring composition of the present invention is preferably 5,000 to 100,000, and more preferably from the viewpoint of dispersibility, developability, reworkability, and resistance. 7,000 to 50,000. When the weight average molecular weight is less than 5,000, the pigment dispersibility and coating film resistance are deteriorated, and when it is more than 100,000, not only the developability and reworkability are deteriorated, but also the viscosity of the photosensitive coloring composition is high. Too much, handling and coatability will deteriorate.

  Since the resin used in the photosensitive coloring composition of the present invention exhibits an excellent dispersion effect in almost all pigments, a color filter is obtained using the photosensitive coloring composition of the present invention in which the pigment is dispersed with this resin. When the filter segment is formed, a filter segment with less pigment aggregates can be obtained.

  The resin used in the photosensitive coloring composition of the present invention can be used at a ratio of 30 to 800 parts by weight with respect to 100 parts by weight of the pigment. When the amount is less than 30 parts by weight, sufficient dispersion stability cannot be obtained. When the amount is more than 800 parts by weight, the pigment concentration and the film thickness required for the color filter cannot be compatible.

<Dye>
As a pigment | dye used for the photosensitive coloring composition which concerns on the colored layer of this invention, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. The pigment is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposability, and an organic pigment is usually used.

  Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown by a color index (CI) number.

  The red coloring composition for forming the red filter segment includes red pigments such as CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1. 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, and 272 can be used. A yellow pigment and an orange pigment can be used in combination with the red coloring composition.

  Examples of yellow pigments added to the red coloring composition include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 71,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194, and 199 or the like can be used. Of these, C.I. Pigment Yellow 138, 139, 150, and 185 are preferred.

  As the orange pigment added to the red coloring composition, for example, C.I. Pigment orange 36, 43, 51, 55, 59, 61, and 71 can be used.

  In the green coloring composition for forming the green filter segment, for example, C.I. Pigment Green 7, 10, 36, 37, and 58 can be used as a green pigment. A yellow pigment can be used in combination with the green coloring composition.

  Examples of yellow pigments added to the green coloring composition include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 71,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194, and 199 or the like can be used. Of these, C.I. Pigment Yellow 138, 139, 150, and 185 are preferred.

  Blue coloring compositions for forming blue filter segments include, for example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60 as blue pigments. , And 64 can be used. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination with the blue coloring composition.

  Examples of the yellow coloring composition for forming the yellow filter segment include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20. 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 Yellow pigments such as 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, and 199 can be used. .

  Orange pigments such as C.I. Pigment orange 36, 43, 51, 55, 59, 61, and 71 can be used for the orange coloring composition for forming the orange filter segment.

  Blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 are used for the cyan coloring composition for forming the cyan filter segment. be able to.

  For the magenta coloring composition for forming the magenta color filter segment, for example, purple pigments such as CI Pigment Violet 1 and 19 and red pigments such as CI Pigment Red 144, 146, 177, 169 and 81 are used. be able to. The magenta colored composition can be used in combination with the same yellow pigment as the yellow colored composition for forming the yellow color filter segment.

  In addition, in order to ensure good coatability, sensitivity, developability, and the like while balancing saturation and lightness, an inorganic pigment can be used in combination with the organic pigment. Inorganic pigments include yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green and other metal oxide powders, metal sulfide powders, metal powders, etc. Can be mentioned. Furthermore, for color matching, a dye can be contained within a range that does not lower the heat resistance. In addition, the photosensitive coloring composition of the present invention finely disperses the pigment in the photosensitive coloring composition using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, and a paint conditioner. Can be manufactured.

  Next, as black pigments for the light shielding layer, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 900 manufactured by Mitsubishi Chemical Corporation are used. 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Curve Corporation, Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, manufactured by Asahi Carbon Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa Carbon black ColorBlack Fw200, ColorBl ck Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack350, PrintexU, PrintexV, Printex140U, Printex140V (both trade names), and the like.

  The photosensitive coloring composition of the present invention can contain a dispersant for dispersing the pigment. The dispersant is excellent in dispersing the pigment, and since the effect of preventing reaggregation of the pigment after dispersion is great, a composition obtained by dispersing the pigment in the photosensitive coloring composition using the dispersant is excellent in transparency. Color filters can be obtained. As the dispersant, a resin-type pigment dispersant, a dye derivative, a surfactant, or the like is used. Although the addition amount of a dispersing agent is not specifically limited, From a viewpoint of a dispersibility and a color characteristic with respect to 100 weight part of pigment | dyes, Preferably it is 0.1-40 weight part, More preferably, it is 0.1-30. It can be used in parts by weight.

  The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the resin, and adsorbs to the pigment to stabilize the dispersion of the pigment into the photosensitive coloring composition. It works to do. Resin-type pigment dispersants include polyurethanes, polyacrylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polycarboxylic acid esters Siloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) and polyesters having a free carboxyl group, their salts, etc. Used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and the like Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are also used. These can be used alone or in admixture of two or more.

  Commercially available resin-type pigment dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, manufactured by Big Chemie. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen SOLSPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32, manufactured by Nippon Lubrizol Co., Ltd. 00, 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402 manufactured by Efka Chemicals , 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503, and the like.

  A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used, and these can be used alone or in admixture of two or more.

<Photopolymerization initiator>
The photosensitive coloring composition of the present invention contains a photopolymerization initiator.

As a photopolymerization initiator,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2 An acetophenone photopolymerization initiator such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyldimethyl ketal;
Benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4′-methyldiphenyl sulfide;
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-pienyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, and 2,4-trichloromethyl (4′-methoxystyryl) -6-to Triazine-based photopolymerization initiators such as lyazine;
Borate photopolymerization initiator;
A carbazole photoinitiator; and
An imidazole photopolymerization initiator or the like is used.

  A photoinitiator can be used in the amount of 5-200 weight part with respect to 100 weight part of pigment | dyes in a photosensitive coloring composition, Preferably it is 10-150 weight part.

  The above photopolymerization initiators can be used alone or in admixture of two or more. As the sensitizer, α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10- Phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4′-diethylamino A compound such as benzophenone can also be used in combination. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator in the photosensitive coloring composition.

<Polymerizable monomer>
A polymerizable monomer is added to the photosensitive coloring composition of the present invention.

As a polymerizable monomer,
Monofunctional monomers such as (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, acrylonitrile, cyclohexyl (meth) acrylate, and tricyclodecanyl (meth) acrylate;
1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene Glycol di (meth) acrylate, di (meth) acrylate of other polyalkylene glycols, di (meth) acrylates of various polyester diols, di (meth) acrylates of various polyurethane diols, di (meth) acrylates of EO-modified bisphenol A, And bifunctional monomers such as di (meth) acrylates of various bifunctional epoxy compounds; and
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tri (meth) acrylate of various isocyanurates, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) And polyfunctional monomers such as acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylate of various polyfunctional epoxy resins, and caprolactone-modified dipentaerythritol hexaacrylate, but not limited thereto. Also, it may be used alone or in combination of two or more.

  A polymerizable monomer can be used in the ratio of 20-200 weight part with respect to 100 weight part of pigment | dyes.

<Solvent>
Examples of the organic solvent contained in the photosensitive coloring composition of the present invention include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl Alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate , Ethylene glycol monopropyl ether, ethylene glycol monohexyl ether Ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol Acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol Monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether Acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate Acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and secondary but dibasic acid ester and the like, without being limited thereto, used alone or as a mixture of two or more. The organic solvent can be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, with respect to 100 parts by weight of the dye in the photosensitive coloring composition.

  The photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition.

Examples of storage stabilizers include:
Quaternary ammonium chlorides such as benzyltrimethylammonium chloride and diethylhydroxyamine hydrochloride;
Organic acids such as lactic acid and oxalic acid;
Methyl ester of the organic acid;
catechols such as t-butylpyrocatechol and pyrocatechol;
Organic phosphines such as tetraethylphosphine and tetraphenylphosphine; and
Examples thereof include phosphite.

  The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the dye in the photosensitive coloring composition.

  Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

As a silane coupling agent,
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane;
(meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane;
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3, Epoxy silanes such as 4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane; and
and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the dye in the photosensitive coloring composition.

  The photosensitive coloring composition of the present invention can be prepared as gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent developing type or alkali developing type colored resist material. The solvent development type or alkali development type colored resist material is obtained by dispersing a dye in a composition containing a resin, a photopolymerization initiator, a polymerizable monomer, and an organic solvent.

  The photosensitive coloring composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust.

<Color filter>
Next, the color filter of the present invention will be described.

  The color filter of the present invention is a color filter having a filter segment formed using the photosensitive coloring composition of the present invention. The color filter includes an additive color mixture comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, And a subtractive color type with at least one yellow filter segment.

  The color filter of this invention can be manufactured by forming the filter segment of each color on a transparent substrate by the photolithographic method using the photosensitive coloring composition of this invention.

  As the transparent substrate, a glass plate or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.

  The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared as the solvent developing type or alkali developing type colored resist material has a dry film thickness of 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. Apply to 2-5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkali developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.

  In development, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

  In order to increase the photosensitivity by UV exposure, a film that prevents polymerization inhibition by oxygen by applying and drying a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin after coating and drying the colored resist material. Ultraviolet exposure can also be performed after forming.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the photolithography method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a transparent substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. is there. The transfer method is a method in which a color filter layer is formed in advance on the surface of a peelable transfer base sheet, and this color filter layer is transferred to a desired transparent substrate.

EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
First, preparation of the acrylic resin solution used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(Preparation of resin solution 1)
370 parts of propylene glycol monomethyl ether acetate is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.

Paracumylphenol ethylene oxide modified acrylate
("Aronix M110" manufactured by Toa Gosei Co., Ltd.) 10.0 parts 2-Methacryloyloxyethylphthalic acid
(“NK Ester CB-1” manufactured by Shin-Nakamura Chemical Co., Ltd.) 50.0 parts benzyl methacrylate 40.0 parts azobisisobutyronitrile 3.5 parts After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then azobisiso A solution in which 1.0 part of butyronitrile was dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 15,000.

  After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 30%. An acrylic resin solution was prepared.

(Preparation of resin solution 2)
370 parts of propylene glycol monomethyl ether acetate is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.

Paracumylphenol ethylene oxide modified acrylate 20.0 parts Glycidyl methacrylate 24.5 parts Benzyl methacrylate 16.8 parts Azobisisobutyronitrile 2.1 parts After the addition, the reaction was further carried out at 100 ° C for 3 hours, followed by azobisisobuty A solution prepared by dissolving 1.0 part of nitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.3 part of trisdimethylaminophenol and 0.1 part of hydroquinone are added to 12.4 parts of acrylic acid (100 mol% of glycidyl group) in the container, at 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5 mgKOH / g, the reaction was terminated to obtain an acrylic resin solution. Further, 26.3 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl group) and 0.3 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 15,000.

  After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 30% in the previously synthesized resin solution. Acetate was added to prepare an acrylic resin solution.

(Preparation of resin solution 3)
The resin solution 2 was synthesized in the same manner as the resin solution 2 except that dicyclopentanyl methacrylate (“Fancryl FA-513M” manufactured by Hitachi Chemical Co., Ltd.) was used in preparation of the resin solution 2, and the solid content was 30%. An acrylic resin solution was prepared. The weight average molecular weight of this acrylic resin solution was 15000.

(Preparation of resin solution 4)
370 parts of propylene glycol monomethyl ether acetate is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.

Paracumylphenol ethylene oxide modified acrylate 6.0 parts Glycidyl methacrylate 34.1 parts Benzyl methacrylate 6.0 parts Azobisisobutyronitrile 1.5 parts After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then azobisisobuty A solution prepared by dissolving 1.0 part of nitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone are added to 17.3 parts of acrylic acid (100 mol% of glycidyl group), and the container is heated to 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5 mgKOH / g, the reaction was terminated to obtain an acrylic resin solution. Further, 36.5 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 15000.

  After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate so that the non-volatile content was 30% in the previously synthesized resin solution. Was added to prepare an acrylic resin solution.

(Preparation of resin solution 5)
370 parts of propylene glycol monomethyl ether acetate is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.

Paracumylphenol ethylene oxide modified acrylate 3.0 parts Glycidyl methacrylate 36.9 parts Benzyl methacrylate 2.0 parts Azobisisobutyronitrile 1.5 parts After the dropwise addition, the reaction was further carried out at 100 ° C for 3 hours, and then azobisisobuty A solution prepared by dissolving 1.0 part of nitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are added to 18.7 parts of acrylic acid (100 mol% of glycidyl group) in the container, at 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5 mgKOH / g, the reaction was terminated to obtain an acrylic resin solution. Further, 39.4 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 15000.

  After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate so that the non-volatile content was 30% in the previously synthesized resin solution. Was added to prepare an acrylic resin solution.

(Preparation of resin solution 6)
370 parts of propylene glycol monomethyl ether acetate is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.

Paracumylphenol ethylene oxide-modified acrylate 50.0 parts Glycidyl methacrylate 0.8 parts Benzyl methacrylate 48.0 parts Azobisisobutyronitrile 3.5 parts After the addition, the reaction was further carried out at 100 ° C for 3 hours, and then azobisisobuty A solution prepared by dissolving 1.0 part of nitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air substitution, and 0.1 part of trisdimethylaminophenol and 0.1 part of hydroquinone are added to 0.4 part of acrylic acid (100 mol% of glycidyl group) in the container, at 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5 mgKOH / g, the reaction was terminated to obtain an acrylic resin solution. Further, 0.8 parts of tetrahydrophthalic anhydride (100 mol% of the generated hydroxyl group) and 0.1 part of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 15000.

  After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate so that the non-volatile content was 30% in the previously synthesized resin solution. Was added to prepare an acrylic resin solution.

(Preparation of resin solution 7)
370 parts of propylene glycol monomethyl ether acetate is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator is added dropwise over 1 hour at the same temperature to conduct a polymerization reaction Went.

Paracumylphenol ethylene oxide-modified acrylate 20.0 parts Methacrylic acid 15.0 parts Benzyl methacrylate 65.0 parts Azobisisobutyronitrile 3.5 parts After the addition, the reaction is further carried out at 100 ° C for 3 hours, and then azobisisobutyrate. A solution obtained by dissolving 1.0 part of nitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 15,000.

  After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 30%. An acrylic resin solution was prepared.

(Preparation of resin solution 8)
Synthesis was performed in the same manner as for the resin solution 7 except that benzyl methacrylate was changed to dicyclopentanyl methacrylate in the preparation of the resin solution 7 to prepare an acrylic resin solution having a solid content of 30%. The weight average molecular weight of this acrylic resin solution was 15000.

(Preparation of resin solution 9)
Synthesis was performed in the same manner as in the resin solution 2 except that benzyl methacrylate was changed to methyl methacrylate in the preparation of the resin solution 2 to prepare an acrylic resin solution having a solid content of 30%. The weight average molecular weight of this acrylic resin solution was 15000.

(Preparation of resin solution 10)
The resin solution 2 was synthesized in the same manner as in the resin solution 2 except that the paracumylphenol ethylene oxide modified acrylate was changed to phenol ethylene oxide modified acrylate (Osaka Organic Chemical Co., Ltd. “Biscoat # 192”). A 30% acrylic resin solution was prepared. The weight average molecular weight of this acrylic resin solution was 15000.

(Preparation of resin solution 11)
The resin solution 7 was synthesized in the same manner as the resin solution 7 except that paracumylphenol ethylene oxide-modified acrylate and benzyl methacrylate were changed to methyl methacrylate to prepare an acrylic resin solution having a solid content of 30%. The weight average molecular weight of this acrylic resin solution was 15000.

(Preparation of resin solution 12)
The resin solution 7 was synthesized in the same manner as the resin solution 7 except that paracumylphenol ethylene oxide modified acrylate was changed to phenol ethylene oxide modified acrylate and benzyl methacrylate was changed to 2-hydroxyethyl methacrylate. An acrylic resin solution was prepared. The weight average molecular weight of this acrylic resin solution was 15000.

(Preparation of resin solution 13)
The resin solution 7 was synthesized in the same manner as the resin solution 7 except that the paracumylphenol ethylene oxide modified acrylate was changed to phenol ethylene oxide modified acrylate and the methacrylic acid was changed to dicyclopentanyl methacrylate. An acrylic resin solution was prepared. The weight average molecular weight of this acrylic resin solution was 15000.

(Preparation of resin solution 14)
The resin solution 2 was synthesized in the same manner as the resin solution 2 except that dicyclopentanyl methacrylate was used as the paracumylphenol ethylene oxide-modified acrylate to prepare an acrylic resin solution having a solid content of 30%. The weight average molecular weight of this acrylic resin solution was 15000.

[Preparation of photosensitive coloring composition]
Table 1 shows the CI CI numbers of pigments, the types of components, and the contents in weight percent in the photosensitive coloring compositions used in Examples 1 to 30 and Comparative Examples 1 to 12.

  First, a pigment, a dispersant (“Solsperse 20000” manufactured by Nippon Lubrizol), a resin solution, and a solvent (propylene glycol monomethyl ether acetate) are mixed and dispersed in a planetary ball mill using zirconia beads to disperse the pigment. The bodies (R-1 to R-10, G-1 to G-10, and B-1 to B-10) were prepared.

Subsequently, as shown in Table 2, the pigment dispersions (R-1 to R-10, G-1 to G-10, and B-1 to B-10) were added to the resin solution (1 to 13), polymerizable property. Monomer (dipentaerythritol hexaacrylate), photopolymerization initiator (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone) , A sensitizer (2,4-diethylthioxanthone), and a solvent (propylene glycol monomethyl ether acetate) were stirred and mixed, and then filtered through a 1 μm filter to prepare photosensitive coloring compositions (R01 to R10, G01 to G10, B01). -B10, CR01-CR04, CG01-CG04, and CB01-CB04).

[Evaluation of photosensitive coloring composition]
About the photosensitive coloring composition (R01-R10, G01-G10, B01-B10, CR01-CR04, CG01-CG04, and CB01-CB04) obtained in each of Examples 1-30 and Comparative Examples 1-12, the following The dispersion stability, developability, and reworkability were evaluated by the above method. The results are shown in Table 3.

(Dispersion stability evaluation)
The viscosity at 25 ° C. of the photosensitive coloring composition thus prepared was measured at an rpm of 20 rpm using an E-type viscometer (TUE-20L type manufactured by TOKI SANGYO). The viscosity on the day of preparation of the photosensitive coloring composition was measured by measuring the initial viscosity (η0: mPa · s) and the viscosity after storage for 7 days in a constant temperature room at 40 ° C (η7: mPa · s). Sex was evaluated according to the following criteria.

○: η7 / η0 is less than 1.20, almost no increase in viscosity occurs, and dispersion stability is good. Δ: η7 / η0 is 1.20 or more and less than 1.50, and a slight increase in viscosity is observed. Slightly inferior

(Developability evaluation)
The photosensitive coloring composition was spin-coated on a 10 × 10 cm transparent glass substrate, pre-baked at 70 ° C. for 20 minutes to form a coating film having a dry film thickness of about 2.0 μm, and the film thickness (T1) was measured. Subsequently, the film was exposed to ultraviolet light at an exposure amount of 50 mJ, developed with an alkali developer for 50 seconds, the film thickness (T2) after development was measured, and the film thickness ratio (T2 / T1) was calculated.

    The evaluation criteria were as follows.

○: Film thickness ratio (T2 / T1) 0.95 or more ×: Film thickness ratio (T2 / T1) less than 0.95

(Reworkability evaluation)
The coating film-formed substrate used for the evaluation of developability was post-baked at 230 ° C. for 90 minutes.

  A rework solution heated to 65 ° C. (Semi-Clean DF-7 manufactured by Yokohama Oils and Fats Industry) was prepared in a petri dish, and the obtained film-formed substrate cut into 1.5 cm square was immersed for 5 minutes. After 5 minutes, the substrate together with the rework liquid was transferred from the petri dish to a round bottom flask, and the rework liquid containing the peeled coating film was filtered with a filter paper, and the size of the peeled piece developed on the filter paper was measured with an optical microscope with a dimension measuring function. It measured using.

  The measurement conditions are as follows. First, measure 10 points from the longest part of the peeled piece in the center of the filter paper at the center of the optical microscope, concentrically up and down, left and right, and the longest part of the peeled piece, and obtain the average value of the longest part. It was.

  The evaluation criteria are as follows.

A: Dissolution (There is no peeling piece that can be confirmed with an optical microscope.)
○: Average length of peeled piece is less than 300 μm △: Average length of peeled piece is from 300 μm to less than 500 μm ×: Average length of peeled piece is from 500 μm to less than 1000 μm XX: Average length of peeled piece is at least 1000 μm

  The photosensitive coloring compositions of Comparative Examples 1 to 12 have good long-term storage stability and developability, but the reworkability is poor, whereas the photosensitive coloring compositions of Examples 1 to 30 of the present invention are: It was found that reworkability was excellent while maintaining long-term storage stability and developability.

Claims (6)

In the photosensitive coloring composition comprising a resin, a dye, a photopolymerization initiator, a polymerizable monomer, and a solvent, the resin is a structural unit represented by the following general formula (1) ( a), the structural unit having a carboxyl group (b), and I vinyl polymer der composed of structural units having no other hydroxyl group (c), the structural unit (b) is a compound represented by the following general formula ( 2):

(In General Formula (2), R ⁴ is a hydrogen atom or a methyl group, and X ¹ is General Formula (3):

[In General Formula (3), R ⁵ is an alkylene group having 2 to 12 carbon atoms, and m is an integer of 1 or 2. ]
Y ¹ is a group represented by the general formula (4):

[In General Formula (4), R ⁶ is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 6 to 8 carbon atoms, or an arylene group having 2 to 14 carbon atoms, and n is 0 or 1 It is an integer. ] Is a group represented by )
The structural unit (b1) and / or main chain represented by the following general formula (5):

(In the general formula (5), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a glycidyl group, a methyl glycidyl group, a 3,2-glycidoxyethyl group, a 3,4-epoxycyclohexyl group, 3 , 4-epoxybutyl group or 4,5-epoxypentyl group.)
A photosensitive coloring composition characterized in that it is a structural unit (b2) obtained by adding an unsaturated monobasic acid to the structural unit (d) represented by formula (I) and adding a polybasic acid anhydride to the generated hydroxyl group. object.
General formula (1):

(In General Formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and R ³ may have a hydrogen atom or a benzene ring. It is a good alkyl group having 1 to 20 carbon atoms, and l is an integer of 1 to 15.) When the resin copolymerizes the main chain, the precursor (a ′) of the structural unit (a) is 1 to 35% by weight, the precursor (d ′) of the structural unit (d) is 4 to 75% by weight, An unsaturated monobasic acid was added to a resin obtained by copolymerizing 1 to 75% by weight of the precursor (c ′) of the unit (c), and then a polybasic acid anhydride was added to the generated hydroxyl group. photosensitive coloring composition according to claim 1, characterized in that the resin. 3. The photosensitive coloring composition according to claim 1, wherein the precursor (a ′) of the structural unit (a) contains ethylene oxide or propylene oxide-modified (meth) acrylate of paracumylphenol. . The precursor of the structural unit (c) (c ') is, (meth) photosensitive coloring composition according to claim 1 to 3 any one of claims, characterized in that it includes an acrylic acid alkyl ester. The precursor (c ′) of the structural unit (c) is benzyl (meth) acrylate and / or dicyclopentanyl (meth) acrylate and / or dicyclopentenyl (meth) acrylate and / or cyclopentanyloxyethyl ( The photosensitive coloring composition according to any one of claims 1 to 4 , comprising (meth) acrylate. Color filter characterized by comprising filter segments and / or black matrix are formed of claims 1-5 photosensitive coloring composition according to any one.