KR101642844B1 - Photosensitive colored composition for color filter and color filter - Google Patents

Abstract

The photosensitive coloring composition contains a resin, a colorant, a photopolymerization initiator, a polymerizable monomer, and a solvent. The resin is a vinyl-based polymer composed of a constituent unit (a) represented by the following formula (1), a carboxyl group-containing constituent unit (b) and a constituent unit (a)

(Formula 1)

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and 1 is 1 ≪ / RTI >

A photosensitive coloring composition, a color filter, a colorant, a photopolymerization initiator, a polymerizable monomer

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive coloring composition and a color filter for a color filter,

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

2. Description of the Related Art In recent years, liquid crystal display devices have been applied to television monitor applications, PC monitor applications, and mobile applications, and pigment dispersion type color filters are widely used as color filters used in such applications. In preparing the pigment dispersion type color filter, a photosensitive coloring composition obtained by adding a photopolymerizable monomer and a polymerization initiator to a coloring composition obtained by dispersing a pigment in a resin (acrylic resin or the like) using a dispersant, a solvent, , A photolithography method in which a colored coating film such as a colored layer or a light shielding layer is formed and patterned is widely used. The patterned coating film is post-baked at a high temperature of 200 ° C or more to impart resistance in a subsequent process.

In addition, as the liquid crystal display device has been made more general-purpose, the price of the product has been greatly reduced. And a reduction in the cost of the color filter has recently become an issue. Recently, a glass substrate having a coloring film after post-baking in which problems have occurred is recycled and reused (hereinafter referred to as " rework "), (Hereinafter referred to as " reworkability is good ") is one of the effective and easy means of reducing the cost.

As a means of reworking, there is a method in which a colored coating film that has been patterned as a color filter and is post-baked is peeled off from the glass substrate by using a redeposition solution, and the photosensitive coloring composition is applied to the glass substrate again. The coating film on the glass substrate after post-baking has high heat resistance and solvent resistance, and in order to rework, a strong alkaline solution of high temperature and high concentration should generally be used as the rework solution. It is necessary not only to peel the colored coating film of the color filter after patterning post-baking at the time of reworking from the glass substrate but also to prevent clogging of the remover solution circulated through the filter for collecting the peeling pieces, .

Patent Document 1 discloses a photosensitive coloring composition containing a carboxyl group and a resin having no hydroxyl group. By using this resin, the above-mentioned reworkability is improved. However, the photosensitive coloring composition containing this resin has poor dispersion stability of the pigment, and insufficient long-term storage stability.

Patent Document 2 discloses a photosensitive coloring composition using a resin having an alkylene group substituted with a benzene ring at a side chain or at a terminal thereof in order to improve the long-term storage stability of the photosensitive coloring composition. In this composition, the adsorption / orientation property to the pigment surface is improved by the effect of the pi electron of the benzene ring, and exhibits excellent pigment dispersibility. However, in the photosensitive coloring composition containing this resin, the coating film of the color filter after patterned post-baking is not peeled off initially due to the influence of the thermosetting reaction in the post-baking after patterning, or even if the peeling- Resulting in clogging of the filter, resulting in poor reworkability.

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

[Prior Art Literature]

[Patent Literature]

Patent Document 1: JP-A-10-171119

Patent Document 2: Japanese Patent Application Laid-Open No. 2004-101728

The present invention relates to a photosensitive coloring composition that both achieves excellent reworkability and long-term storage stability and does not impair basic performance such as developability, and a color filter comprising a filter segment and / or a black matrix formed using the same. And the like.

The above object is achieved by a photosensitive coloring composition comprising a resin, a colorant, a photopolymerization initiator, a polymerizable monomer and a solvent, wherein the resin comprises a structural unit (a) represented by the following general formula (1) ) And a structural unit (c) other than the structural unit (a) and the structural unit (b).

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, An integer of 1 to 15).

In a preferred embodiment of the present invention, the structural unit (b)

(Wherein R < ⁴ > is a hydrogen atom or a methyl group, and X < ^{1 &}

Wherein R ⁵ is an alkylene group having 2 to 12 carbon atoms, m is an integer of 1 or 2, and Y ¹ is a group represented by the formula (4)

Wherein R ⁶ is an alkylene group having 2 to 20 carbon atoms in the main chain, a cycloalkylene group having 6 to 8 ring carbon atoms, or an arylene group having 6 to 14 ring carbon atoms, and n is Is an integer of 0 or 1), and / or a structural unit (b1) represented by the general formula (5)

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a glycidyl group, a methylglycidyl group, a 3,2-glycidoxyethyl group, a 3,4-epoxycyclohexyl group, a 3,4- Is a structural unit (b2) obtained by adding an unsaturated monobasic acid to the structural unit (d) represented by the general formula (1) or (2) above and adding a polybasic acid anhydride to the resulting hydroxyl group.

In a preferred aspect of the present invention, the constituent unit (c) has no hydroxyl group.

In a preferred embodiment of the present invention, the resin comprises 1 to 35% by weight of the precursor (a ') of the structural unit (a), 10 to 90% by weight of the precursor (b') of the structural unit and 1 to 75% by weight of the precursor (c ') of the general formula (c).

In a preferred embodiment of the present invention, the resin comprises 1 to 35% by weight of the precursor (a ') of the structural unit (a), 4 to 75% by weight of the precursor (d') of the structural unit And 1 to 75% by weight of a precursor (c ') of the unit (c), and then adding a polybasic acid anhydride to the resulting hydroxyl group.

In a preferred embodiment of the present invention, the precursor (a ') of the structural unit (a) contains ethylene oxide and / or propylene oxide-modified (meth) acrylate of para-cumylphenol.

In a preferred embodiment of the present invention, the precursor (c ') of the constituent unit (c) contains a (meth) acrylic acid alkyl ester.

In a preferred embodiment of the present invention, the precursor (c ') of the structural unit (c) is at least one selected from the group consisting of benzyl (meth) acrylate and / or dicyclopentanyl (meth) acrylate and / or dicyclopentenyl And / or cyclopentanyloxyethyl (meth) acrylate.

The present invention also provides a color filter characterized by comprising a filter segment and / or a black matrix formed from the photosensitive coloring composition of the present invention.

By using the photosensitive coloring composition having a good reworkability of the present invention, the waste of the glass substrate in the production of the color filter can be reduced, and a color filter of low cost can be obtained.

(Mode for carrying out the invention)

The photosensitive coloring composition of the present invention contains a resin, a colorant, a photopolymerization initiator, a polymerizable monomer, and a solvent. Hereinafter, each component will be described in detail. In the present specification and claims, the terms "(meth) acrylic acid", "(meth) acrylate" and "(meth) acryloyloxy" refer to "acrylic acid and / or methacrylic acid" Acrylate and / or methacrylate ", and " acryloyloxy and / or methacryloyloxy ". Likewise, the term " (meth) acrylamide " means " acrylamide and / or methacrylamide ".

<Resin>

The resin contained in the photosensitive coloring composition of the present invention is a resin having a structural unit (a) represented by the following general formula (1), a structural unit (b) having a carboxyl group and a structural unit (c) other than the structural units Based polymer. The constituent unit (a) functions as a solvent affinity site, the constituent unit (b) functions as a pigment adsorbing site and the alkali soluble site, and the constituent unit (c) Is a constitutional unit necessary for obtaining physical properties as a coloring coating film which can not be attained only by the above method.

(Formula 1)

Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, Lt; / RTI &gt;

In the present invention, a resin satisfying the following characteristics is used.

(1) Dispersibility

Which can prevent agglomeration of the pigment as a coloring agent in the coloring composition and keep the pigment finely dispersed for a long period of time.

(2) Developability

Capable of removing only the unexposed portion with an (alkaline) developing solution at the time of development.

(3) Re-workability

And the colored coating film after post-baking can be removed by (strongly alkaline) rework solution, so that the peeling off of the colored coating film does not become coarse.

In order to satisfy both of these characteristics, it is necessary to balance the constituent unit (a), the constituent unit (b) and the constituent unit (c), to maintain the dispersion stability of the pigment as a colorant, Alkaline) developer penetrates to swell only the unexposed portion and react with the carboxyl group of the unexposed portion to partially remove it and remove it. In the rework, the (highly alkaline) reworking liquid penetrates into the exposed portion to swell the exposed portion , It is important to carry out the resin design so as to be able to react with the carboxyl group and partially remove it by solubilization.

It is also important in terms of production efficiency to design the coating film in consideration of the balance of the constituent unit (a), the constituent unit (b) and the constituent unit (c) so that the removed coating film flows out as finely as possible to the developer and the workpiece solution .

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

The constituent unit (a) effectively functions as a solvent affinity site in the side chain alkylene moiety of the π electrons of the side chain benzene ring and an appropriate length. The side chain benzene ring has a function of promoting the adsorption of the resin to the pigment and suppressing aggregation of the pigment in order to orient the pigment as a coloring agent. Therefore, the dispersion of the pigment surface-treated with the resin having the constituent unit (a) can maintain high storage stability.

When the constituent unit (a) functions as a pigment surface adsorption site at the time of pigment dispersion and the constituent unit (b) having a carboxyl group reacts with alkali at the time of development or rework to become an alkali-soluble site, Since the constituent unit (a) functions as a site which is not soluble in alkali, the balance between the hydrophilicity and the hydrophobicity of the part to be removed is good and is liable to be in the form of fine particles.

In Formula (1), the alkyl group of R ³ has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group includes not only a straight chain alkyl group, but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the alkyl group of R ³ has 1 to 10 carbon atoms, the alkyl group is disturbed to inhibit the approach of the resins to each other to promote adsorption / orientation to the pigment. When the number of carbon atoms is more than 10, the effect of steric hindrance of the alkyl group increases, The adsorption / orientation of the benzene ring to the pigment is also inhibited. This tendency becomes remarkable 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 lowered. 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 the side chain benzene ring, the solvent affinity and the pigment orientation property are further improved, and not only the dispersibility of the pigment as a coloring agent but also the developability and the workability are improved.

Examples of the precursor (a ') of the structural unit (a) include ethylene oxide (EO) modified (meth) acrylate of phenol, EO or propylene oxide (PO) modified (meth) acrylate of paraumylphenol, EO (Meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol. 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) acrylates of para-cumylphenol have not only the effect of the π-electron of the benzene ring but also the steric effect thereof to form a better adsorption / It is most preferable.

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

The structural unit (b) having a carboxyl group functions as a pigment adsorber at the time of dispersing the pigment as a colorant, as an alkali-soluble group at the unexposed portion at the time of development, and as a strong alkali-soluble group at the exposed portion during rework.

Examples of the precursor (b ') of the structural unit (b) having a carboxyl group include carboxyl groups such as unsaturated dicarboxylic acids such as (meth) acrylic acid, crotonic acid,? -Chloroacrylic acid, maleic acid, maleic anhydride and fumaric acid, And a compound having an ethylenically unsaturated double bond.

Particularly preferred as the structural unit (b) having a carboxyl group is a structure obtained by adding an unsaturated monobasic acid to the structural unit (b1) represented by the following general formula (2) and / or the structural unit (d) (B2) obtained by adding a polybasic acid anhydride to one hydroxyl group. The constituent unit (b1) is obtained by copolymerizing the precursor (b1 ') with another precursor, and the constituent unit (d) is obtained by copolymerizing the precursor (d') with another precursor.

(2)

(Wherein R &lt; ⁴ &gt; is a hydrogen atom or a methyl group, and X &lt; ^{1 &}

(Formula 3)

Wherein R ⁵ is an alkylene group having 2 to 12 carbon atoms, m is an integer of 1 or 2, and Y ¹ is a group represented by the formula (4)

(Formula 4)

Wherein R ⁶ is an alkylene group having 2 to 20 carbon atoms in the main chain, a cycloalkylene group having 6 to 8 ring carbon atoms, or an arylene group having 6 to 14 ring carbon atoms, and n is Is an integer of 0 or 1)])

(Formula 5)

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a glycidyl group, a methylglycidyl group, a 3,2-glycidoxyethyl group, a 3,4-epoxycyclohexyl group, a 3,4- Or a 4,5-epoxypentyl group.)

Specific examples of the alkylene group having 2 to 12 carbon atoms represented by R ⁵ in the general formula (3) include -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.

In the general formula (4), R ⁶ is an alkylene group having 2 to 20 carbon atoms in the main chain (that is, a straight-chain portion connecting the carbonyl carbon atom in the formula 4 and the carbonyl carbon atom in the formula 2) Or a cycloalkylene group having 6 to 14 ring carbon atoms, or an arylene group having 6 to 14 ring carbon atoms. Here, the alkylene group having 2 to 20 carbon atoms in the main chain is preferably an alkylene, alkenyl, cycloalkyl, cycloalkenyl, dialkyl, alkynyl, A cycloalkylene group having 6 to 8 ring carbon atoms and an arylene group having 6 to 14 ring carbon atoms may be substituted with an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a di An alkyl group, an alkynyl group, an alkynylphenyl group, an alkynylallyl group, an aromatic substituent, a nitro group, a halogen element and the like.

Examples of the alkylene group having 2 to 20 carbon atoms in the main chain include -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH (CH ₃ ) -, -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 ] -, -CH ₂ -CH [(CH ₂ ) ₁₇ CH ₃ ] - and the like. The alkylene group having 2 to 20 carbon atoms in the main chain preferably has 2 to 20 carbon atoms in total.

Examples of the cycloalkylene group having 6 to 8 ring carbon atoms include the cycloalkylene groups shown by the following chemical formulas 6 to 9, and the cycloalkylene groups represented by the chemical formulas An alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, a dialkyl group, an alkynyl group, an alkynylphenyl group, an alkynylallyl group, an aromatic substituent, a nitro group, a halogen element and the like.

Examples of the arylene group having 6 to 14 ring carbon atoms include an arylene group represented by the following formulas (10) to (13), and the arylene group represented by any of these formulas An alkynyl group, an alkynyl allyl group, an aromatic substituent, a nitro group, a halogen atom, and the like may be substituted as a substituent.

Preferred examples of the precursor (b1 ') of the constituent unit (b1) having a carboxyl group from the viewpoint of balance between the developability and the reworkability include acrylic acid dimer [R ⁵ : -CH ₂ -CH ₂ -], ) Acrylate [R ⁵ : -CH ₂ -CH ₂ -], 2- (meth) acryloyloxyethylsuccinic acid [R ⁵ : -CH ₂ -CH ₂ -, R ⁶ : -CH ₂ -CH ₂ -] (Meth) acryloyloxyethylphthalic acid [R ⁵ : -CH ₂ -CH ₂ -, R ⁶ : phenylene group], 2- (meth) acryloyloxyethylhexahydrophthalic acid [R ⁵ : -CH ₂ -CH ₂ -, R ^6: a cyclohexylene group], 2- (meth) acryloyl one oxy acid profile _{^{[R 5: -CH 2 -CH (}} CH 3) -, R 6: -CH 2 -CH 2 (Meth) acryloyloxypropylphthalic acid [R ⁵ : -CH ₂ -CH (CH ₃ ) -, R ⁶ : phenylene group], 2- (meth) acryloyloxypropylhexahydrophthalic acid [ _{^{R 5: -CH 2 -CH (CH}} 3) -, R 6: a cyclohexylene group; and polyethylene oxide-modified succinic acid (meth) acrylate _{^{[R 5: -CH 2 -CH 2}} -, R 6: -CH 2 -CH ₂ -], ω- carboxy - (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. The precursor (b ') is not limited to the above examples, and may be used alone or in combination of two or more.

The constituent unit (b2) can also be obtained by polymerizing the precursor (d ') by copolymerizing the precursor (b') obtained by adding an unsaturated monobasic acid to the precursor (d ') and adding a polybasic acid anhydride to the resulting hydroxyl group, (d), adding an unsaturated monobasic acid, and adding a polybasic acid anhydride to the resulting hydroxyl group. More specifically, the precursor (d ') has an epoxy group, which reacts with a carboxyl group of an unsaturated monobasic acid to form an ester, and a hydroxyl group is formed, and the hydroxyl group is converted to a carboxyl group of a polybasic acid anhydride To produce an ester.

Examples of the precursor (d ') of the structural unit (d) represented by the formula (5) include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2- glycidoxyethyl (meth) 4 epoxybutyl (meth) acrylate, and 3,4 epoxycyclohexyl (meth) acrylate. These may be used alone or in combination of two or more. From the viewpoint of reactivity with an unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of the unsaturated monobasic acid to be added to the constituent unit (d) include (meth) acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, haloalkyl at the alpha position of (meth) acrylic acid, alkoxyl, halogen, And the like. Examples of the polybasic acid anhydride which reacts with the hydroxyl group of the addition reaction product include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride and maleic anhydride. May be used alone or in combination of two or more.

For the purpose of increasing the number of carboxyl groups in the constituent unit (b '), if necessary, a tricarboxylic acid anhydride such as trimellitic anhydride or the like may be used, or a tetracarboxylic acid 2 such as pyromellitic dianhydride The remaining anhydride group may be hydrolyzed using an anhydride.

The carboxyl group of the constituent unit (b1) and / or the constituent unit (b2) is separated from the main chain of the copolymer (resin) relative to the carboxyl group of the constituent unit polymerized from a precursor such as (meth) acrylic acid, The obstacle is small. Therefore, swelling, reaction, and dissolution proceed smoothly because the penetration of the work solution (strong alkaline aqueous solution) into the coated film having increased crosslink density by exposure is fast and the compatibility is good.

In the photosensitive coloring composition of the present invention, a functional group which reacts with a carboxyl group is present and the functional group thereof reacts with a part of the carboxyl groups of the constituent unit (b1) and / or the constituent unit (b2) Since the crosslinking point is deviated, the penetration of the rework solution into the coating film is not hindered, and the coating film is smoothly removed.

The precursor (c ') of the constituent unit (c) is not particularly limited as long as it does not use a functional group reactive with the carboxyl group before the developing step,

(Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Linear or branched alkyl (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate and lauryl

Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and cyclopentanyl (meth) acrylate;

Benzyl (meth) acrylate, and alkyl (meth) acrylates having an aromatic ring such as phenyl (meth) acrylate;

(Meth) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate;

Alkoxy (poly) alkylene glycol (meth) acrylates such as methoxy (poly) propylene glycol (meth) acrylate and ethoxy (poly) ethylene glycol (meth) acrylate;

(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (Meth) acrylamides such as immorpholine;

Styrenes such as styrene and? -Methylstyrene;

Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;

Fatty acid vils such as vinyl acetate and vinyl propionate;

Vinyl monomers having a carboxyl group other than the precursor (b ') such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and crotonic acid;

(Meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate, and cyclohexanedimethanol mono (Meth) acrylate, and alkyl-? -Hydroxyalkyl acrylates such as ethyl? -Hydroxymethylacrylate; alkyl (meth) acrylates having a hydroxyl group such as hydroxyalkyl

(Poly) alkylene glycol (meth) acrylates such as (poly) propylene glycol (meth) acrylate and (poly) ethylene glycol (meth) acrylate; Acrylates such as N- (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (Hydroxyalkyl) (meth) acrylamide, (meth) acrylamides having a hydroxyl group;

Vinyl ether compounds having a hydroxyl group such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, and 2- (or 3- or 4-) hydroxybutyl vinyl ether;

Allyl having a hydroxyl group such as 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and hydroxyalkyl allyl ether such as 2- (or 3- or 4-) Ethers;

(Meth) acrylates having two hydroxyl groups such as glycerol mono (meth) acrylate;

N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) Alkyl (meth) acrylates having an N, N-dialkylamino group such as acrylate; And

(Meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (Meth) acrylamides having N, N-dialkylamino groups such as acrylamide, and the like. These may be used singly or in combination of two or more. However, the present invention is not limited thereto.

The structural unit (c) is a structural unit necessary for obtaining physical properties as a colored coating film that can not be achieved by only the structural unit (a) and the structural unit (b). The constituent unit (c) preferably has no hydroxyl group. When the constituent unit (c) has a hydroxyl group, the dehydration condensation reaction with the carboxyl group of the constituent unit (b) occurs by the heat treatment of the coating film, resulting in an increase in the crosslinking density of the ester bond, to be. From the viewpoint of the film formability, the precursor (c ') of the constituent unit (c) is preferably alkyl (meth) acrylate. Among them, from the viewpoint of pigment dispersibility, stability and coating film resistance, benzyl / Or dicyclopentanyl (meth) acrylate is more preferable.

In the case of copolymerizing the precursor (a '), the precursor (b') and the precursor (c ') in order to obtain the resin contained in the photosensitive coloring composition of the present invention, polymerization of the precursor (a') with respect to the entire precursor The ratio is preferably 1 to 50% by weight, more preferably 1 to 35% by weight. When the polymerization ratio of the precursor (a ') is less than 1% by weight, the dispersing effect of the pigment as a coloring agent is lowered and a sufficient dispersing effect can not be obtained. On the other hand, if it is more than 50% by weight, the hydrophobicity increases and the compatibility with other components in the photosensitive coloring composition is markedly lowered, resulting in lowering of the developability of the photosensitive coloring composition, occurrence of residues and precipitation of monomers and photopolymerization initiators There is also. The resin having the constituent unit (a) obtained by copolymerizing the precursor (a ') in an amount of 1 to 35% by weight has a favorable compatibility with the constituent unit (b) and the constituent unit (c) Re-workability is demonstrated.

In the case of copolymerizing the precursor (a '), the precursor (b') and the precursor (c ') in order to obtain the resin contained in the photosensitive coloring composition of the present invention, the polymerization of the precursor (b' The ratio is preferably 5 to 91% by weight, more preferably 10 to 90% by weight. When the proportion of the precursor (b ') is less than 5% by weight, sufficient reactivity of the developer or riser solution can not be obtained. On the other hand, if it is more than 91% by weight, the amount of carboxyl groups in the photosensitive composition increases, and structural stability due to hydrogen bonding is caused, and the dispersion stability of the pigment as a coloring agent may be lowered in some cases. The resin having the constituent unit (b) obtained by copolymerizing 10 to 90% by weight of the precursor (b ') has a good balance with the constituent unit (a) and the constituent unit (c) Developability and reworkability are exhibited.

When the precursor (a '), the precursor (b') and the precursor (c ') are copolymerized in order to obtain the resin contained in the photosensitive coloring composition of the present invention, polymerization of the precursor (c') with respect to the entire precursor The ratio is preferably 1 to 80% by weight, more preferably 1 to 75% by weight. When the proportion of the precursor (c ') is less than 1% by weight, sufficient film properties can not be obtained. On the other hand, if it is more than 80% by weight, the content of the constituent unit (a) and the constituent unit (b) decreases, and sufficient dispersibility, developability and reworkability of the pigment as a colorant can not be obtained. The resin having the constituent unit (c) obtained by copolymerizing 1 to 75% by weight of the constituent unit (c) has a good balance with the constituent unit (a) and the constituent unit (b) Developability and reworkability are exhibited.

In the case of copolymerizing the precursor (a '), the precursor (d') and the precursor (c ') in order to obtain the 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 dispersing effect of the pigment as a coloring agent is lowered and a sufficient dispersing effect can not be obtained. On the other hand, if it is more than 50% by weight, the hydrophobicity increases and the compatibility with other components in the photosensitive coloring composition is markedly lowered, resulting in lowering of the developability of the photosensitive coloring composition, occurrence of residues and precipitation of monomers and photopolymerization initiators There is also. The resin obtained by adding the unsaturated monobasic acid and the polybasic acid anhydride to the resin (precursor resin) having the constituent unit (a) obtained by copolymerizing 1 to 35% by weight of the precursor (a ' Is well balanced with the constituent unit (b2) and the constituent unit (c), and excellent developability and leachability are exhibited.

In the case of copolymerizing the precursor (a '), the precursor (d') and the precursor (c ') in order to obtain the resin contained in the photosensitive coloring composition of the present invention, the polymerization ratio of the precursor (d') to the entire precursor Is preferably 2 to 80% by weight, and more preferably 4 to 75% by weight. When the ratio of the precursor (d ') is less than 2% by weight, the unsaturated monobasic acid is added to the resulting copolymer (precursor resin), and the polybasic acid anhydride is added to the resulting hydroxyl group. Can not be obtained. On the other hand, if it is more than 80% by weight, the amount of carboxyl groups in the photosensitive composition is increased, so that structural tensions due to hydrogen bonding are generated and the dispersion stability of the pigment as a coloring agent is sometimes lowered. The resin having the constituent unit (b2) obtained by adding the unsaturated monobasic acid and the polybasic acid anhydride to the resin (precursor resin) having the constituent unit (d) obtained by copolymerizing 4 to 75% by weight of the precursor (d ' The proportion of the constituent unit (b2) is well balanced with the constituent unit (a) and the constituent unit (c), and excellent developability and leachability are exhibited.

In the case of copolymerizing the precursor (a '), the precursor (d') and the precursor (c ') in order to obtain the 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. When the proportion of the precursor (c ') is less than 1% by weight, sufficient film properties can not be obtained. On the other hand, if it is more than 80% by weight, the content of the constituent unit (a) and the content of the constituent unit (b2) decreases, and sufficient dispersibility, developability and reworkability of the pigment as a colorant can not be obtained. The resin obtained by adding the unsaturated monobasic acid and the polybasic acid anhydride to the resin (precursor resin) having the constituent unit (c) obtained by copolymerizing 1 to 75% by weight of the precursor (c ' The balance between the constituent unit (a) and the constituent unit (b2) is good, and excellent developability and leachability are exhibited.

(Meth) acrylate and / or dicyclopentanyl (meth) acrylate and / or dicyclopentanyl (meth) acrylate, which are preferable as the precursor (c ') of the constituent unit (c), from the viewpoints of dispersibility, stability and coating film resistance of the pigment as a colorant. The weight ratio of the chloropentenyl (meth) acrylate and / or the cyclopentanyloxyethyl (meth) acrylate is preferably in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the entire precursor (including unsaturated monobasic acid and polybasic acid anhydride when formed from the constituent unit (d) , Preferably 1 to 80% by weight. If the amount is less than 1% by weight, physical properties of the coating film are not sufficient. If the amount is more than 80% by weight, the dispersibility, developability, and workability of the pigment as a colorant are poor because the constituent unit (a) .

The polymerization ratio of benzyl (meth) acrylate and / or dicyclopentanyl (meth) acrylate, which is preferable as the precursor (c ') of the constituent unit (c), is preferably from Is preferably 1 to 65% by weight in the total precursor (including unsaturated monobasic acid and polybasic acid anhydride when formed from the constituent unit (d)). When the content of the structural unit (a) and the content of the structural unit (b) is less than 1 wt%, the physical properties of the coating film are insufficient, while when it is more than 65 wt%, the dispersibility, developability, .

The resin contained in the photosensitive coloring composition of the present invention is obtained by reacting the precursor (a '), the precursor (b') and the precursor (c ') in the presence of a radical polymerization initiator in an inert gas stream at a temperature of 50 to 150 ° C By radical polymerization over 10 hours. Alternatively, the resin contained in the photosensitive coloring composition of the present invention can be produced by reacting the precursor (a '), the precursor (d') and the precursor (c ') in the presence of a radical polymerization initiator at a temperature of 50 to 150 ° C The reaction atmosphere is replaced with air, hydroquinone is added, the unsaturated monobasic acid is reacted at 50 to 150 DEG C for 2 to 10 hours, triethylamine is added, and a polybasic acid anhydride is added At 50 to 150 占 폚 for 2 to 10 hours. The polymerization reaction may be carried out in the presence of a solvent, if necessary.

Examples of the radical polymerization initiator include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, ditertiary butyl peroxide and t-butyl peroxybenzoate, Azo compounds such as azobisisobutyronitrile, and the like, but the present invention is not limited thereto, and two or more kinds of azo compounds may be used in combination. The radical polymerization initiator is used in a proportion of preferably 1 to 20 parts by weight based on 100 parts by weight of the total precursor of the resin.

Examples of the solvent that can be used in the radical polymerization include water and / or a water-miscible organic solvent, acetic acid esters such as ethyl cellosolve acetate and propylene glycol monomethyl ether acetate; Ketones such as cyclohexanone and methyl isobutyl ketone; Xylene, ethylbenzene and the like can be used. Examples of the water-miscible organic solvent include alcohol solvents such as ethanol, isopropyl alcohol and n-propyl alcohol, and mono or dialkyl ethers of ethylene glycol or diethylene glycol. However, the organic solvent is not limited to these, Two or more types may be used in combination.

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 from the viewpoints of dispersibility, developability, workability and resistance of the pigment as a colorant, 7,000 to 50,000. If the weight average molecular weight is less than 5,000, the pigment dispersibility and coating film resistance deteriorate. If the weight average molecular weight is more than 100,000, not only the developability and reworkability are deteriorated but also the viscosity of the photosensitive coloring composition is excessively high and handling and coating properties are deteriorated .

Since the resin used in the photosensitive coloring composition of the present invention exhibits excellent dispersing effect, almost all the pigments exhibit excellent dispersing effect. Therefore, by using the photosensitive coloring composition of the present invention in which the pigment as the coloring agent is dispersed by the resin, When formed, a filter segment with a small pigment aggregate can be obtained.

The resin used in the photosensitive coloring composition of the present invention can be used in a proportion of 30 to 800 parts by weight based on 100 parts by weight of the colorant (pigment). If the amount is less than 30 parts by weight, sufficient dispersion stability can not be obtained. If the amount is more than 800 parts by weight, the colorant (pigment) concentration required for the color filter and the film thickness can not be compatible.

<Colorant>

As the colorant to be used in the photosensitive coloring composition of the present invention, organic or inorganic pigments may be used singly or in combination of two or more. The pigment is preferably a pigment having a high coloring property and a high heat resistance, particularly a pigment having high heat decomposability, and an organic pigment is usually used.

Specific examples of organic pigments usable in the photosensitive coloring composition of the present invention are represented by color index (CI) numbers.

48: 3, 48: 4, 81: 1, 2: 1, 2: 1, , 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, , 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, and 272. A yellow pigment and an orange pigment may be used in combination in the red coloring composition.

Examples of the yellow pigment 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, , 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, 171, 172 , 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, and 199. Among them, C.I. Pigment Yellow 138, 139, 150, and 185 are preferred.

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

Green pigments such as C.I. Pigment Green 7, 10, 36, 37, and 58 may be used for the green coloring composition for forming the green filter segments. A yellow pigment may be used in combination with the green coloring composition.

Examples of yellow pigments to be 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, , 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, 171, 172 , 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, and 199. Among them, C.I. Pigment Yellow 138, 139, 150, and 185 are preferred.

15: 2, 15: 3, 15: 4, 15: 6, 16, 22 and 60 as blue pigments , And 64 may be used. The violet pigment such as C. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 may 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, , 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, 171, 172, 173, , 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194 and 199 can be used.

The orange coloring composition for forming the orange filter segment may include, for example, orange pigments such as C. I. Pigment Orange 36, 43, 51, 55, 59, 61, and 71.

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

Examples of the magenta coloring composition for forming the magenta filter segment include purple pigments such as CI Pigment Violet 1 and 19 and red pigments such as CI Pigment Red 144, 146, 177, 169, and 81 . The yellow coloring composition for forming a yellow color filter segment and the same yellow pigment may be used in combination in the magenta coloring composition.

It is also possible to use inorganic pigments in combination with the above organic pigments in order to ensure good coating properties, sensitivity, and developability while balancing chroma and brightness. Examples of the inorganic pigments include metal oxides such as yellow lead, zinc sulfide, red oxide (red iron oxide (III)), cadmium titanate, ultramarine blue, persulfate, chromium oxide and cobalt rust, metal sulfides and metal powders. Further, for coloring, the dye may be contained within a range not lowering the heat resistance. The photosensitive coloring composition of the present invention can be produced by finely dispersing a coloring agent in a photosensitive coloring composition using various dispersion means such as 3 roll mill, 2 roll mill, sand mill, kneader, stirrer, paint conditioner and the like .

Next, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, and MCF88 of Mitsubishi Chemical Corporation , # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 3050, # 3750, # 3950, diamond black A, diamond black N220M, diamond black N234, Diamond black I, diamond black LI, diamond blue II, diamond diamond N339, diamond diamond SH, diamond diamond SH, diamond diamond LH, diamond diamond H, diamond black HA, diamond diamond SF, diamond diamond N550M, N, N991, N907, N908, N990, N991, N908, carbon black Asahi # 80 manufactured by Asahi Carbon Co., Ltd., Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # Color Black Fw200, Color Black Fw2, Asahi # 60, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, , Color BIack Fw2V, Color Black Fw1, Color Black Fw18, Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 250, Special Black 350, Printex U, Printex V , Printex 140U, Printex 140V (all trade names), and the like.

The photosensitive coloring composition of the present invention may contain a dispersing agent for dispersing the pigment as a coloring agent. The dispersing agent is excellent in the dispersion of the pigment and has a large effect of preventing the re-aggregation of the pigment after dispersion, so that the composition comprising the pigment dispersed in the photosensitive coloring composition using the dispersing agent can provide a color filter having excellent transparency. As the dispersing agent, a resin type pigment dispersing agent, a pigment derivative, a surfactant and the like are used. The amount of the dispersant to be added is not particularly limited, but it is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the colorant (pigment) have.

The resinous pigment dispersant has a pigment affinity site having a property of adsorbing to the pigment and a site compatible with the resin and adsorbed to the pigment to stabilize the dispersion of the pigment in the photosensitive colorant composition. Examples of the resinous pigment dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamines An amide or a salt thereof formed by the reaction of a polysiloxane, a long chain polyaminoamide phosphate, a hydroxyl group-containing polycarboxylic acid ester, a modified product thereof, a poly (lower alkyleneimine) and a polyester having a liberated carboxyl group Is used. Further, 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, Polyester-based, modified polyacrylate, and ethylene oxide / propylene oxide adducts are also used. These may be used alone or in combination of two or more.

As a commercially available resin type pigment dispersant, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 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, 32000, 32500, 32600, 34750, 36600, 38500, 41000, 41090 , EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, 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. The organic pigments also include pale yellow aromatic polycyclic compounds such as naphthalene-based or anthraquinone-based pigments, which are generally not referred to as pigments. Examples of the pigment derivative include those described in Japanese Patent Laid-Open Nos. 63-305173, 57-15620, 59-40172, 63-17102, and 5-9469 These may be used singly or in combination of two or more.

<Photopolymerization initiator>

The photosensitive coloring composition of the present invention includes a photopolymerization initiator.

As the photopolymerization initiator,

(4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxynaphthoacetophenone, 4-t-butyldichloroacetophenone, Acetophenone-based photopolymerization initiator such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)

Benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl 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) (Trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) - s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6 (4-methoxy-naphth- Triazine-based photopolymerization initiators such as triazine, triazine, and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine;

A borate-based photopolymerization initiator;

A carbazole-based photopolymerization initiator; And

An imidazole-based photopolymerization initiator, and the like.

The photopolymerization initiator may be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the colorant (pigment) in the photosensitive coloring composition.

The photopolymerization initiator may be used alone or in admixture of two or more. Examples of the sensitizer include? -Acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, and 4,4'-diethylaminobenzophenone May be used in combination. The sensitizer may be used in an amount of 0.1 to 60 parts by weight based on 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 the polymerizable monomer,

Monofunctional monomers such as (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, acrylonitrile, cyclohexyl (meth) acrylate, and tricyclodecanyl (meth) acrylate;

(Meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di Di (meth) acrylates of various poly (alkylene glycol) di (meth) acrylates, di (meth) acrylates of various poly Di (meth) acrylates of EO-modified bisphenol A, and di (meth) acrylates of various bifunctional epoxy compounds; And

(Meth) acrylate of trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, various isocyanurates, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate of dipentaerythritol hexa (meth) acrylate, various polyfunctional epoxy resins, and caprolactone-modified dipentaerythritol hexaacrylate (meth) acrylate, And the like. However, the present invention is not limited to these, and two or more kinds of monomers may be used in combination.

The polymerizable monomer may be used in a proportion of 20 to 200 parts by weight based on 100 parts by weight of the colorant (pigment).

<Solvent>

Examples of the organic solvent included 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, Methylene-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, 3- 3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutylacetate , N-butyl alcohol, n-butylbenzene, n-propyl alcohol, isopropyl alcohol, n-butyl acetate, But are not limited to, acetates, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p- Benzene,? -Butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono tertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, Propylene 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 Dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl 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 Glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, Acid iso-butyl, and the like, but propyl acetate, and dibasic acid ester, is not limited to these, they are used alone or in combination, or two or more species. The organic solvent may be used in an amount of 800 to 4000 parts by weight, preferably 1000 to 2500 parts by weight, based on 100 parts by weight of the colorant (pigment) in the photosensitive coloring composition.

The photosensitive coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time.

As the storage stabilizer, for example,

Quaternary ammonium chlorides such as benzyltrimethylammonium chloride and diethylhydroxyamine hydrochloride;

Organic acids such as lactic acid, and oxalic acid;

Methyl esters of said organic acids;

t-butyl pyrocatechol, and pyrocatechol;

Organic phosphines such as tetraethylphosphine, and tetraphenylphosphine; And

Phosphites, and the like.

The storage stabilizer may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the colorant in the photosensitive coloring composition.

In order to improve the adhesion to the transparent substrate, adhesion promoting agents such as a silane coupling agent may be contained.

As the silane coupling agent,

Vinylsilanes such as vinyltris (? -Methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane;

(meth) acrylsilanes such as? -methacryloxypropyltrimethoxysilane; ? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? - (3,4-epoxycyclohexyl) methyltrimethoxysilane, ,? - (3,4-epoxycyclohexyl) methyltriethoxysilane,? -glycidoxypropyltrimethoxysilane, and? -glycidoxypropyltriethoxysilane;

(Aminoethyl)? - aminopropyltrimethoxysilane, N -? (Aminoethyl)? - aminopropyltriethoxysilane, N -? Amino silanes such as aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane, N-phenyl-? -Aminopropyltrimethoxysilane, and N-phenyl-? -Aminopropyltriethoxysilane; And

mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

The silane coupling agent may 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 colorant (pigment) in the photosensitive coloring composition.

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

The photosensitive coloring composition of the present invention can be obtained by a method such as centrifugation, sintering filter, membrane filter or the like, by using coarse particles of 5 탆 or more, preferably coarse particles of 1 탆 or more, more preferably coarse particles of 0.5 탆 or more, It is preferable to carry out the removal.

<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 a additive color mixture type having 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 mixture type having at least one yellow color filter segment.

The color filter of the present invention can be produced by forming a filter segment of each color on a transparent substrate by using the photosensitive coloring composition of the present invention by photolithography.

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

The formation of each color filter segment by the photolithography method is performed by the following method. That is, the photosensitive coloring composition prepared as the above solvent-developing or alkali-developing type coloring resist material is applied onto a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, Mu m. The dried film is subjected to ultraviolet exposure through a mask having a predetermined pattern formed in contact or noncontact state with the film. Thereafter, a desired pattern is formed by dipping in a solvent or an alkaline developing solution, or spraying a developing solution by spraying or the like to remove un-hardened portions, and then the same operation can be repeated for a different color to produce a color filter. Heating may also be carried out if necessary in order to accelerate the polymerization of the colored resist material. According to the photolithography method, a color filter having higher precision than the printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide or the like is used as an alkali developing solution, and organic alkalis such as dimethylbenzylamine and triethanolamine may be used. A defoaming agent or a surfactant may be added to the developer.

Further, in order to increase photosensitivity by ultraviolet exposure, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried after coating and drying the colored resist material to prevent polymerization inhibition by oxygen After the film is formed, ultraviolet ray exposure may be performed.

The color filter of the present invention can be manufactured by electrodeposition, transfer, or the like in addition to the photolithography method. The electrodeposition method is a method of producing a color filter by electrodepositing colloidal particles on a transparent conductive film by electrodeposition of each color filter segment using a transparent conductive film formed on a transparent substrate. The transfer method is a method in which a color filter layer is previously formed on the surface of a releasable transfer base sheet and the color filter layer is transferred onto a desired transparent substrate.

When a problem is found in the production process of the color filter of the present invention, the color filter is peeled off from the substrate surface using a peeling liquid (hereinafter referred to as a recycling liquid) containing a highly concentrated strong alkaline solution, It can be reused (reworked).

As a criterion of the rework performance, the solubility of the coating film of the photosensitive coloring composition baked at 230 캜 for 60 minutes with respect to 100 g of the recycled solution at 65 캜 is 30 to 120 mg. If it is smaller than 30 mg, it is not peeled off or the peeling-off is large, which causes clogging of the liquid of the recycling liquid used for circulation, resulting in poor efficiency. If it is larger than 120 mg, it is peeled off even in weakly alkaline solution, so that the development is too rapid and a high-precision color filter can not be formed. By virtue of the synergistic effect of the constituent unit (a), the constituent unit (b) and the constituent unit (c) of the resin of the present invention, the solubility is 30 to 120 mg,

The rework solution used here has high pH (pH 11 or higher), KOH and / or NaOH, organic alkali, hydrophilic solvent, surfactant, and water. Specific examples thereof include PK-CFR 310, PK-CFR 320 and PK-CFR 370 manufactured by PARKER CORPORATION, Semiclin DF-7 and EP-10 manufactured by Yokohama Yushi Kogyo K.K., And the like.

(Example)

Hereinafter, the present invention will be described in more detail with reference to examples, but the following examples do not limit the scope of the present invention at all. In the examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

First, the preparation of the acrylic resin solution used in Examples and Comparative Examples will be described. The molecular weight of the acrylic resin in the acrylic resin solution is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

<Preparation of acrylic resin solution 1>

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide-modified acrylate

(Aronix M110 manufactured by Toagosei Co., Ltd.) 10.0 parts

2-methacryloyloxyethylphthalic acid

("NK Ester CB-1" manufactured by Shin Nakamura Kagaku Co., Ltd.) 50.0 parts

Benzyl methacrylate 40.0 parts

Azobisisobutyronitrile 3.5 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour to obtain a solution of an acrylic resin. 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 DEG C for 20 minutes to measure the non-volatile content. Based on the measured value, cyclohexanone To prepare an acrylic resin solution 1.

&Lt; Preparation of acrylic resin solution 2 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide modified acrylate 20.0 parts

24.5 parts of glycidyl methacrylate

Benzyl methacrylate 16.8 parts

Azobisisobutyronitrile 2.1 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Subsequently, 0.3 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 12.4 parts of acrylic acid (100 mol% of glycidyl group) in the vessel, and the reaction was continued at 120 DEG C for 6 hours to obtain a solid content The reaction was terminated at a point of time of 0.5 mgKOH / g to obtain a solution of an acrylic resin. Subsequently, 26.3 parts of tetrahydrophthalic anhydride (100 mol% of the resulting hydroxyl group) and 0.3 part of triethylamine were added and reacted at 120 DEG C for 3.5 hours to obtain a solution of an acrylic resin. 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 占 폚 for 20 minutes to measure the nonvolatile content. Based on the measured value, Glycol monomethyl ether acetate was added thereto to prepare an acrylate resin solution 2.

<Preparation of acrylic resin solution 3>

Synthesis was carried out in the same manner as in the acrylic resin solution 2 except that benzyl methacrylate was changed to dicyclopentyl methacrylate ("Pancuril FA-513M" available from Hitachi Chemical Co., Ltd.) in the preparation of the acrylic resin solution 2, Of acrylic resin solution 3 was prepared. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 4 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol 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. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Subsequently, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 17.3 parts of acrylic acid (100 mol% of glycidyl group) in the vessel, and the reaction was continued at 120 DEG C for 6 hours, When the acid value became 0.5 mgKOH / g, the reaction was terminated to obtain a solution of the acrylic resin. Subsequently, 36.5 parts of tetrahydrophthalic anhydride (100 mol% of the produced hydroxyl group) and 0.5 part of triethylamine were added and reacted at 120 DEG C for 3.5 hours to obtain a solution of an acrylic resin. 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with propylene glycol mono And methyl ether acetate was added thereto to prepare an acrylic resin solution 4.

&Lt; Preparation of acrylic resin solution 5 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide modified acrylate 3.0 parts

36.9 parts of glycidyl methacrylate

Benzyl methacrylate 2.0 parts

Azobisisobutyronitrile 1.5 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Subsequently, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 18.7 parts of acrylic acid (100 mol% of glycidyl group), and the reaction was continued at 120 캜 for 6 hours, When the acid value became 0.5 mgKOH / g, the reaction was terminated to obtain a solution of the acrylic resin. Subsequently, 39.4 parts of tetrahydrophthalic anhydride (100 mol% of the resulting hydroxyl group) and 0.5 part of triethylamine were added and reacted at 120 DEG C for 3.5 hours to obtain a solution of an acrylic resin. 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with propylene glycol mono Methyl ether acetate was added to prepare an acrylic resin solution 5.

&Lt; Preparation of acrylic resin solution 6 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Paracumyl Phenol Ethylene Oxide Modified Acrylate 50.0 parts

Glycidyl methacrylate 0.8 part

Benzyl methacrylate 48.0 parts

Azobisisobutyronitrile 3.5 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Subsequently, 0.1 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added into the above vessel, and the reaction was continued at 120 캜 for 6 hours, and the solid content The reaction was terminated at a point of time of 0.5 mgKOH / g to obtain a solution of an acrylic resin. Subsequently, 0.8 part of tetrahydrophthalic anhydride (100 mol% of the produced hydroxyl group) and 0.1 part of triethylamine were added and reacted at 120 DEG C for 3.5 hours to obtain a solution of an acrylic resin. 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with propylene glycol mono Methyl ether acetate was added to prepare an acrylic resin solution 6.

&Lt; Preparation of acrylic resin solution 7 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide modified acrylate 20.0 parts

Methacrylic acid 15.0 parts

Benzyl methacrylate 65.0 parts

Azobisisobutyronitrile 3.5 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour to obtain a solution of an acrylic resin. 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 DEG C for 20 minutes to measure the non-volatile content. Based on the measured value, cyclohexanone Was added to prepare an acrylic resin solution 7.

&Lt; Preparation of acrylic resin solution 8 >

Synthesis was conducted in the same manner as in the acrylic resin solution 7 except that benzyl methacrylate was changed to dicyclopentanyl methacrylate in the preparation of the acrylic resin solution 7 to prepare an acrylic resin solution 8 having a solid content of 30%. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 9 >

Synthesis was conducted in the same manner as in the acrylic resin solution 2 except that benzyl methacrylate was changed to methyl methacrylate in the preparation of the acrylic resin solution 2 to prepare an acrylic resin solution 9 having a solid content of 30%. The weight average molecular weight of the acrylic resin was about 15,000.

<Preparation of acrylic resin solution 10>

Synthesis was carried out in the same manner as in the acrylic resin solution 2 except that the paraxylphenol ethylene oxide-modified acrylate was changed to phenol ethylene oxide-modified acrylate ("Viscot # 192" manufactured by Osaka Yuki Kagaku) in the preparation of the acrylic resin solution 2 To prepare an acrylic resin solution 10 having a solid content of 30%. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 11 >

Synthesis was conducted in the same manner as in the acrylic resin solution 7 except that para-cumylphenol ethylene oxide-modified acrylate and benzyl methacrylate were changed to methyl methacrylate in the preparation of the acrylic resin solution 7 to obtain an acrylic resin solution 11 having a solid content of 30% . The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 12 >

Synthesis was carried out in the same manner as in the acrylic resin solution 7 except that paraxylphenol ethylene oxide modified acrylate was changed to phenol ethylene oxide modified acrylate and benzyl methacrylate was changed to 2-hydroxyethyl methacrylate in the preparation of acrylic resin solution 7, To prepare an acrylic resin solution 12 having a solid content of 30%. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 13 >

Synthesis was carried out in the same manner as in the acrylic resin solution 7 except that the paraxylphenol ethylene oxide-modified acrylate was changed to phenol ethylene oxide-modified acrylate and the methacrylic acid was changed to dicyclopentanyl methacrylate in the preparation of the acrylic resin solution 7, 30% acrylic resin solution 13 was prepared. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 14 >

Synthesis was conducted in the same manner as in the acrylic resin solution 2 except that the paraxylphenol ethylene oxide modified acrylate was changed to dicyclopentanyl methacrylate in the preparation of the acrylic resin solution 2 to prepare an acrylic resin solution 14 having a solid content of 30% . The weight average molecular weight of the acrylic resin was about 15,000.

<Preparation of acrylic resin solution 15>

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide-modified acrylate

(Aronix M110 manufactured by Toagosei Co., Ltd.) 30.0 parts

2-methacryloyloxyethylphthalic acid

("NK Ester CB-1" manufactured by Shin Nakamura Kagaku Co., Ltd.) 20.0 parts

Benzyl methacrylate 50.0 parts

Azobisisobutyronitrile 3.5 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour to obtain a solution of an acrylic resin. 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 DEG C for 20 minutes to measure the non-volatile content. Based on the measured value, cyclohexanone To prepare an acrylic resin solution 15.

&Lt; Preparation of acrylic resin solution 16 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide-modified acrylate

(Aronix M110 manufactured by Toagosei Co., Ltd.) 30.0 parts

2-methacryloyloxyethylphthalic acid

("NK Ester CB-1" manufactured by Shin Nakamura Kagaku Co., Ltd.) 20.0 parts

Benzyl methacrylate 35.0 parts

2-hydroxyethyl methacrylate 15.0 parts

Azobisisobutyronitrile 3.5 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour to obtain a solution of an acrylic resin. 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with cyclohexane And an acrylic resin solution 16 was prepared.

&Lt; Preparation of acrylic resin solution 17 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the mixture was heated to 80 DEG C while introducing nitrogen gas into the vessel, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide-modified acrylate

(&Quot; V # 315 &quot; manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) 17.5 parts

Glycidyl methacrylate 28.0 parts

Benzyl methacrylate 10.5 parts

Azobisisobutyronitrile 2.0 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Subsequently, 0.5 g of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 14.2 parts of acrylic acid (100% of glycidyl group) and 0.1 part of hydroquinone were charged into the vessel, and the reaction was continued at 120 캜 for 6 hours, When the acid value became 0.5, the reaction was terminated to obtain a solution of the acrylic resin. Further, 29.9 parts of tetrahydrophthalic anhydride (100% of the produced hydroxyl group) and 0.5 part of triethylamine were added and reacted at 120 DEG C for 3.5 hours to obtain a solution of an acrylic resin. 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with propylene glycol mono Methyl ether acetate was added to prepare an acrylic resin solution 17.

&Lt; Preparation of acrylic resin solution 18 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide-modified acrylate

(V # 315 manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) 18.3 parts

Glycidyl methacrylate 29.3 parts

Benzyl methacrylate 11.0 parts

Azobisisobutyronitrile 2.0 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Next, 0.1 part of trisdimethylaminophenol and 0.1 part of hydroquinone were charged into 14.8 parts of acrylic acid (100% of glycidyl group) and 0.1 part of hydroquinone were charged into the vessel, and the reaction was continued at 120 캜 for 6 hours, When the acid value became 0.5, the reaction was terminated to obtain a solution of the acrylic resin. Further, 26.6 parts of tetrahydrophthalic anhydride (85% of the hydroxyl groups formed) and 0.1 part of triethylamine were added and reacted at 120 DEG C for 3.5 hours to obtain a solution of the acrylic resin. 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with propylene glycol mono Methyl ether acetate was added to prepare an acrylic resin solution 18.

<Preparation of acrylic resin solution 19>

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide-modified acrylate

(V # 315, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) 5.3 parts

Glycidyl methacrylate 37.0 parts

Benzyl methacrylate 5.3 parts

Azobisisobutyronitrile 1.7 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Subsequently, 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 18.8 parts of acrylic acid (100% of glycidyl group) in the vessel, and the reaction was continued at 120 DEG C for 6 hours to obtain a solid content 0.5, the reaction was terminated to obtain a solution of the acrylic resin. Subsequently, 33.7 parts (85% of the hydroxyl groups formed) of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C for 3.5 hours to obtain a solution of an acrylic resin. 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with propylene glycol mono Methyl ether acetate was added to prepare an acrylic resin solution 19.

&Lt; Preparation of acrylic resin solution 20 >

370 parts of propylene glycol monomethyl ether acetate was added to the reaction vessel, and the vessel was heated to 80 DEG C while introducing nitrogen gas, and a mixture of the following monomers and a thermal polymerization initiator was added dropwise over one hour to effect polymerization reaction.

Para-cumylphenol ethylene oxide-modified acrylate

(V # 315, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) 50.0 parts

Glycidyl methacrylate 3.3 parts

Benzyl methacrylate 42.1 parts

Azobisisobutyronitrile 3.3 parts

After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours. Then, 1.0 part of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone, and the reaction was further continued at 100 ° C for 1 hour. Then, 0.1 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 1.7 liters of acrylic acid (100% of glycidyl group), and the reaction was continued at 120 캜 for 6 hours. The solid content 0.5, the reaction was terminated to obtain a solution of the acrylic resin. Subsequently, 3.0 parts of tetrahydrophthalic anhydride (85% of the produced hydroxyl group) and 0.1 part of triethylamine were added and reacted at 120 DEG 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 캜 for 20 minutes to measure the non-volatile content. Based on the measured value, the resin solution synthesized first was mixed with propylene glycol mono Methyl ether acetate was added to prepare an acrylic resin solution 20.

<Preparation of acrylic resin solution 21>

Synthesis was conducted in the same manner as in the acrylic resin solution 17 except that benzyl methacrylate was changed to dicyclopentyl methacrylate ("Pancuril FA-513M" manufactured by Hitachi Chemical Co., Ltd.) in the preparation of the acrylic resin solution 17, % Acrylic resin solution 21 was prepared. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 22 >

Synthesis was carried out in the same manner as in the acrylic resin solution 17 except that the paraxylphenol ethylene oxide-modified acrylate was changed to phenol EO-modified acrylate (Aronix M102 made by Toagosei Co., Ltd.) in the preparation of the acrylic resin solution 17, % Of acrylic resin solution 22 was prepared. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 23 >

Synthesis was conducted in the same manner as in the acrylic resin solution 20 except that the paraxylphenol ethylene oxide-modified acrylate was changed to dicyclopentanyl methacrylate in the preparation of the acrylic resin solution 20 to prepare an acrylic resin solution 23 having a solid content of 30% . The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 24 >

Synthesis was carried out in the same manner as in the acrylic resin solution 16 except that the paraxylphenol ethylene oxide-modified acrylate was changed to phenol EO-modified acrylate and 2-methacryloyloxyethylphthalic acid was changed to methacrylic acid in the preparation of the acrylic resin solution 16 To prepare an acrylic resin solution 24 having a solid content of 30%. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of acrylic resin solution 25 >

Acrylic resin solution 15 was changed to phenol EO-modified acrylate and 2-methacryloyloxyethylphthalic acid was changed to dicyclopentanyl methacrylate in the same manner as the acrylic resin solution 15 To prepare an acrylic resin solution 25 having a solid content of 30%. The weight average molecular weight of the acrylic resin was about 15,000.

&Lt; Preparation of Photosensitive Coloring Composition >

First, the pigment, dispersant, acrylic resin solution and solvent shown in Tables 1A to 1E were mixed with a planetary ball mill using zirconia beads, and the pigment was dispersed to prepare pigment dispersions (R-1 to R-19, G-19, B-1 to B-19, CR-1 to CR-7, CG-1 to CG-7 and CB-1 to CB-7). Further, in Table 1, the blending amount of each component is the proportion (% by weight) in the following coloring composition.

Subsequently, as shown in Tables 2A to 2E, the pigment dispersions (R-1 to R-19, G-1 to G-19, B-1 to B-19, CR-1 to CR- Acrylic resin solution, a polymerizable monomer, a photopolymerization initiator, and a solvent were stirred and mixed with a 1 탆 filter to obtain a photosensitive coloring composition (R01 to R19, G01 to G19, B01 to B19, CR01 to CR07, CG01 to CG07, and CB01 to CB07).

The components in Tables 1A to 1E are as follows.

<Pigment>

P. R. 254: C. I. Pigment Red 254

Irgacure Red BCF manufactured by Chiba Specialty Chemicals

P. R. 177: C. I. Pigment Red 177

Chromobald Red A2B manufactured by Chiba Specialty Chemicals Co.

P. Y. 150: C. I. Pigment Yellow 150

E4GN manufactured by LANXESS

P. G. 36: C. I. Pigment Green 36

Toyo Incy Manufacturers Zeriowon Green 6YK

P. B. 15: 6: C. I. Pigment Blue 15: 6

Toyo Ink SEZO Co., Ltd. Linol Blue ES

P. V. 23: C. I. Pigment Violet 23

Toyo Inkyo Co., Ltd. Lionogen Violet RL

<Dispersant>

"Sol Spurs 20000" manufactured by Nippon Lubrizol Corporation

<Resin solution>

The acrylic resin solution prepared above

<Solvent>

Propylene glycol monomethyl ether acetate

<Polymerizable Monomer>

Dipentaerythritol hexaacrylate

<Photopolymerization initiator>

2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl]

<Increase / decrease>

2,4-diethylthioxanthone

The photosensitive coloring compositions obtained in the above Examples and Comparative Examples were evaluated for dispersion stability, developability, and workability by the following methods. The results are shown in Table 3.

&Lt; Evaluation of dispersion stability &

The viscosity of the photosensitive coloring composition at 25 캜 was measured at 20 rpm using an E-type viscometer (model TUE-20L, manufactured by TOKI SANGYO). The viscosity (? 7 = mPa 占 퐏) of the photosensitive coloring composition after measurement on the day of preparation of the photosensitive coloring composition as initial viscosity? 0 (mPa 占 퐏) and after preservation of the photosensitive coloring composition in a constant temperature room of 40 占 폚 for 7 days was measured, And the viscosity ratio? 7 /? 0 was calculated. Then, the dispersion stability was evaluated based on the following criteria.

?: When? 7 /? 0 is less than 1.20, the viscosity hardly increases and dispersion stability is good

?:? 7 /? 0 was 1.20 or more and less than 1.50, the viscosity was slightly increased, and the dispersion stability was slightly lower

X: When? 7 /? 0 is 1.50 or more, the increase in viscosity is remarkable and dispersion stability is poor.

<Evaluation of Developability>

A photosensitive coloring composition was spin-coated on a transparent glass substrate having a size of 10 x 10 cm and prebaked at 70 DEG C for 20 minutes to form a coating film having a dry film thickness of about 2.0 mu m and the film thickness T1 thereof was measured. Subsequently, the resist film was exposed to ultraviolet light at an exposure dose of 50 mJ and developed with an alkali developer for 50 seconds, and the film thickness (T2) after development was measured to calculate the film thickness ratio (T2 / T1).

Evaluation criteria were as follows.

?: Film thickness ratio (T2 / T1): 0.95 or more

X: film thickness ratio (T2 / T1) less than 0.95

<Evaluation of workability>

The coated film-forming substrate used in the above-described development evaluation was post-baked at 230 캜 for 90 minutes and cut to 1.5 cm in width and length to obtain a sample.

2 mL of a rework solution (Semiclein DF-7 made by Yokohama Yushi Kogyo) heated to 65 ° C was introduced into the shale and the sample was immersed in the rework solution for 5 minutes. After 5 minutes, the sample was transferred from the round bottom flask to the round bottom flask, and the rework solution containing the peeled coating film was filtered with a filter paper having a pore diameter of 5 mu m and a diameter of 3 cm, The size was measured using an optical microscope equipped with a dimensional measurement function.

The measurement conditions were as follows: the length of the longest peeling member was the maximum at five points in total of four points at the same interval on the concentric circle of 1 cm from the center of the filter paper and the center of the filter paper at a magnification of 500 times by an optical microscope; And the average value of the longest portion was obtained.

The evaluation criteria are as follows.

◎: Dissolution (There is no peeling piece which can be confirmed by optical microscope.)

?: The longest average of peeling strips was less than 300 占 퐉

?: The longest part average of the peeled sheet was 300 μm or more and less than 500 μm

X: The longest average of peeling strips was 500 占 퐉 or more and less than 1000 占 퐉

占:: The longest strip average of peeled sheets is 1000 占 퐉 or more

The photosensitive coloring compositions of Comparative Examples 1 to 21 had satisfactory long-term storage stability and developability, but were poor in reworkability, while the photosensitive coloring compositions of Examples 1 to 57 of the present invention retain long-term storage stability and developability In addition, it was found that the workability was also excellent.

Claims (9)

1. A photosensitive coloring composition comprising a resin, a colorant, a photopolymerization initiator, a polymerizable monomer, and a solvent, wherein the resin comprises a structural unit (a) represented by the following formula (1), a structural unit Is a vinyl-based polymer composed of constituent units (c) other than the units (a) and (b) (Formula 1)

(Wherein R ¹ is a hydrogen atom or a methyl group, R ² is an alkylene group having 2 or 3 carbon atoms, R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and 1 is 1 Lt; / RTI &gt; Wherein the structural unit (b) (2)

(Wherein R &lt; ⁴ &gt; is a hydrogen atom or a methyl group, and X &lt; ^{1 &} (Formula 3)

Wherein R ⁵ is an alkylene group having 2 to 12 carbon atoms, m is an integer of 1 or 2, and Y ¹ is a group represented by the formula (4) (Formula 4)

Wherein R ⁶ is an alkylene group having 2 to 20 carbon atoms in the main chain, a cycloalkylene group having 6 to 8 ring carbon atoms, or an arylene group having 6 to 14 ring carbon atoms, and n is Is an integer of 0 or 1), and / or a structural unit (b1) represented by the general formula (5) (Formula 5)

(Wherein R ⁷ is a hydrogen atom or a methyl group, R ⁸ is a glycidyl group, a methylglycidyl group, a 3,2-glycidoxyethyl group, a 3,4-epoxycyclohexyl group, a 3,4- Is a structural unit (b2) obtained by adding an unsaturated monobasic acid to the structural unit (d) represented by the general formula (2) or a 4,5-epoxypentyl group and adding a polybasic acid anhydride to the resulting hydroxyl group A photosensitive coloring composition. delete The photosensitive coloring composition according to claim 1, wherein the structural unit (c) has no hydroxyl group. The positive resist composition according to claim 1, wherein the resin comprises from 1 to 35% by weight of the precursor (a ') of the structural unit (a), from 10 to 90% by weight of the precursor (b' ) Of a precursor (c ') in an amount of 1 to 75% by weight based on the total weight of the composition. The positive resist composition as claimed in claim 1, wherein the resin comprises from 1 to 35% by weight of the precursor (a ') of the constituent unit (a), from 4 to 75% by weight of the precursor (d') of the constituent unit (d) Is a resin obtained by adding an unsaturated monobasic acid to a vinyl copolymer obtained by copolymerizing 1 to 75% by weight of a precursor (c ') of the polyisocyanate compound (c') and then adding a polybasic acid anhydride to the resulting hydroxyl group. The photosensitive coloring composition according to claim 1, wherein the precursor (a ') of the structural unit (a) contains ethylene oxide and / or propylene oxide-modified (meth) acrylate of para-cumylphenol. The photosensitive coloring composition according to claim 1, wherein the precursor (c ') of the constituent unit (c) contains a (meth) acrylic acid alkyl ester. The positive resist composition according to claim 1, wherein the precursor (c ') of the constituent unit (c) is at least one selected from benzyl (meth) acrylate and / or dicyclopentanyl (meth) acrylate and / or dicyclopentenyl Or cyclopentanyloxyethyl (meth) acrylate. A color filter comprising a filter segment and / or a black matrix formed from the photosensitive coloring composition according to any one of claims 1 to 8.