TW201710360A - Curable (meth)acrylate polymer, curable composition, color filter and image display device - Google Patents

Abstract

A curable (meth)acrylate polymer which includes repeating units having a structure in which at least two carboxyl groups are directly bonded to an alicyclic skeleton, and a curable composition and a color filter which include the same.

Description

Curable (meth) acrylate polymer, hardenable composition, color filter, and image display device

The present invention relates to a curable (meth) acrylate polymer, a curable composition containing the polymer, and the use of the polymer to a color filter or the like.

The present application claims priority based on Japanese Patent Application No. 2015-152894, filed on Jan. 31, 2015, the content of which is hereby incorporated herein.

In recent years, from the viewpoint of resource saving or energy saving, photosensitive polymers which can be hardened by active energy rays such as ultraviolet rays or electron beams are widely used in various fields of coating, printing, coating, and adhesives. Composition. Further, in the field of electronic materials such as printed wiring boards, a photosensitive polymer composition which can be cured by an active energy ray is widely used as a solder resist or a photoresist for a color filter.

The color filter is generally a transparent substrate such as a glass substrate; red (R), green (G), and blue (B) patterns formed on the transparent substrate a black matrix formed on the boundary of a pixel; and a protective film formed on a pixel and a black matrix. The color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate.

As a method of forming a pixel and a black matrix (hereinafter referred to as a "coloring pattern" for a pixel and a black matrix), various manufacturing methods have been proposed. In particular, the pigment/dye dispersion method described later provides a coloring pattern which is excellent in durability such as light resistance and heat resistance, and has few defects such as pinholes. The pigment/dye dispersion method is a method of producing a color filter by using a photosensitive polymer composition as a photoresist and repeating the photolithography method of the steps of coating, exposing, developing, and baking. Therefore, the aforementioned pigment/dye dispersion method has become the current mainstream.

In general, the photosensitive polymer composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, and a solvent. As the alkali-soluble resin, polymers of various forms have been developed from the past.

For example, Patent Document 1 discloses a photosensitive material for a color filter using a modified polymer. In the modified polymer, an alicyclic monomer such as tricyclononyl methacrylate or norbornene, and an ethoxylated o-phenylphenol (meth) acrylate (ie, (a) In the copolymer of a (meth) acrylate having a structure derived from an alkylene oxide and an aryl residue represented by 2-phenylphenoxyethyl acrylate, an acid group and a polymerizable unsaturated bond are introduced.

In the method of introducing an acid group and a polymerizable unsaturated bond, the following method is exemplified, and any of the following (1) and (2) is described. In the method, the same performance can be obtained (refer to Example 3 and other examples of Patent Document 2).

(1) A method of reacting a part of an intramolecular acid group of a copolymer with an unsaturated monomer having an epoxy group by prepolymerizing an unsaturated monobasic acid.

(2) A method of pre-polymerizing an epoxy group-containing unsaturated monomer to cause the intramolecular epoxy group of the copolymer to be cleaved with an unsaturated monobasic acid, and reacting the polybasic acid anhydride with the generated hydroxyl group.

The materials obtained in these documents exhibit a certain degree of excellent characteristics from the viewpoints of sensitivity, developability, heat decomposition resistance of a cured product, and heat yellowing resistance. However, the adhesion or flexibility of the cured film to the substrate cannot be said to be sufficient. Moreover, when a dye is used as a coloring material, the original lack of vividness of the dye often occurs.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/141000

[Patent Document 2] Japanese Patent Laid-Open No. 2015-021997

The present invention has been developed in view of the above-described background art, and has been explored for further improvement.

An object of the present invention is to provide heat resistance yellowing and solvent resistance for sensitivity, developability, and cured product when used as a material for a photosensitive polymer composition. A curable (meth) acrylate polymer excellent in adhesion to a substrate, and excellent in dispersibility of a coloring agent, and a method for producing the same.

Further, another object of the present invention is to provide a curable composition of a coating film in order to provide sensitivity, developability, heat-resistant yellowing of a cured product, solvent resistance, adhesion to a substrate, and dispersibility of a dye.

Still another object of the present invention is to provide a curing pattern which is excellent in solvent resistance, adhesion to a substrate, and dispersibility of a coloring agent, and is suitable as a photosensitive polymer for a color filter. A composition, a color filter that provides color tone stability, and a device that provides an image display element having the color filter described above.

In order to solve the above problems, the inventors of the present invention have found that a curable (meth) acrylate polymer having a repeating unit having a structure in which at least two carboxyl groups are directly bonded to an alicyclic skeleton is used. The present invention has been completed in terms of developability, heat-resistant yellowing property as a cured product, solvent resistance, adhesion to a substrate, and dispersibility of a color former.

That is, the first aspect of the invention. It is the following curable (meth) acrylate polymer.

[1] A curable (meth) acrylate polymer characterized by comprising a repeating unit having a structure in which at least two carboxyl groups are directly bonded to an alicyclic skeleton.

The above curable (meth) acrylate polymer preferably has the following characteristics.

[2] The curable (meth) acrylate polymer according to [1], wherein the alicyclic skeleton is a cycloalkane skeleton having 5 to 8 carbon atoms, and a bridged ring having 7 to 11 carbon atoms; At least one of the choices in the skeleton.

[3] The curable (meth) acrylate polymer according to [1] or [2], wherein the alicyclic skeleton is a cyclohexane skeleton, a cycloheptane skeleton, and a bicyclo [3, 2, 0 At least one of the heptane skeletons selected.

[4] The sclerosing (meth) acrylate polymer according to any one of [1] to [3] wherein the repeating unit having a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton is The side chain in the (meth) acrylate polymer has a repeating unit of a hydroxyl group and a monoester of a compound having an alicyclic acid anhydride skeleton and a carboxyl group.

[5] The curable (meth) acrylate polymer according to [4], wherein the above-mentioned repeating unit having a hydroxyl group in a side chain in the (meth) acrylate polymer is a compound for adding an epoxy group A repeating unit obtained by having a repeating unit of a carboxyl group in a side chain.

[6] The curable (meth) acrylate polymer according to [4], wherein the above-mentioned repeating unit having a hydroxyl group in a side chain of the (meth) acrylate polymer is a step of adding a compound having a carboxyl group to the side chain A repeating unit having a repeating unit of an epoxy group.

[7] The curable (meth) acrylate polymer according to any one of [1] to [6] which further contains ethylene derived from a structure which does not contain at least two carboxyl groups directly bonded to the alicyclic skeleton. Repeating unit of carbon-carbon double bond.

[8] The curable (meth) acrylate polymer according to [7], wherein the repeating unit derived from an ethylenic carbon-carbon double bond having no structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton, It is a (meth) acrylate monomer derived from a structure represented by the following formula (3) (In the formula (3), R ⁶ to R ⁸ each represent a hydrogen atom or a methyl group; R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, or a saturated or unsaturated ring which is bonded to each other; wherein * represents a linkage to a (meth) propylene oxime bond site), a decene monomer represented by the following formula (4) (X and Y in the formula (4) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R ¹ and R ² each independently represent a hydrogen atom or a carboxyl group. Or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a cyclic structure in which R ¹ and R ^{2 are} bonded, or a repeating unit of any of a (meth)acrylic monomer and a styrene monomer.

[9] The sclerosing (meth) acrylate polymer according to any one of [1] to [8], wherein the aforementioned repeating unit having an alicyclic skeleton and at least two carboxyl groups is a formula (15)-form ( 19) at least one of the representations,

[10] The curable (meth) acrylate polymer according to any one of [1] to [9], which has a polystyrene-equivalent weight average molecular weight of from 1,000 to 50,000 as measured by gel permeation chromatography. .

The second aspect of the present invention is the following curable composition.

[11] A curable composition comprising the curable (meth) acrylate polymer according to any one of [1] to [10], a solvent, a reactive diluent, a photopolymerization initiator, and a coloring At least one of the agents.

[12] The curable composition according to [11], wherein the colorant is at least one of a dye and a pigment.

The third aspect of the present invention is the following color filter.

[13] A color filter formed using a hardenable composition such as [11] or [12].

The fourth aspect of the present invention is the following image display element.

[14] An image display device comprising the color filter of [13].

[15] A method for producing a curable (meth) acrylate polymer having an alicyclic skeleton in a side chain and at least two carboxyl groups directly bonded to the skeleton, characterized in that: (i) is prepared on the side a step of a chain having a hydroxyl (meth) acrylate polymer, and (ii) a step of reacting a compound having an alicyclic acid anhydride skeleton and a carboxyl group with a hydroxyl group of a (meth) acrylate polymer having a hydroxyl group in a side chain.

[16] The method for producing a curable (meth) acrylate polymer according to [15], wherein the step (i) comprises the steps of: (i-1) preparing a carboxyl group in a side chain (methyl) An acrylate polymer or a step of having a (meth) acrylate polymer having an epoxy group in a side chain; and (i-2) a carboxyl group-addition epoxy compound or a cyclooxy group added thereto A compound of a carboxyl group formed by a (meth) acrylate polymer having a hydroxyl group in a side chain.

Further, the curable composition of the above [11] is preferably a photosensitive polymer composition.

According to the present invention, it is possible to provide heat-resistant yellowing, sensitivity, developability, solvent resistance as a cured product, adhesion to a substrate, and dispersibility of a coloring agent when used as a photosensitive material (methyl group). ) acrylate polymer. Moreover, the cured coating film formed from the photosensitive polymer composition of the present invention is excellent in sensitivity, developability, solvent resistance, adhesion to a substrate, and dispersibility of a coloring agent. Thus, it can be seen that the polymers and compositions of the present invention are extremely valuable in various photoresist fields. In particular, when used as a photosensitive material for a color filter, a color filter type color filter having solvent resistance, adhesion to a substrate, and excellent dispersibility of a dye can be obtained.

Preferred examples of the invention are described in detail below. However, the invention of the present invention is not limited to these examples. Various changes, omissions, combinations, exchanges, and/or additions may be made without departing from the scope of the invention.

As described above, the present invention relates to a curable (meth) acrylate polymer, a curable composition containing the polymer, and the use of the above polymer. More specifically, the present invention relates to a curable (meth) acrylate polymer suitable as a photosensitive material for a color filter, a method for producing the curable (meth) acrylate polymer, and the like. a curable composition of a (meth) acrylate polymer, a photosensitive polymer composition in which a photopolymerization initiator is blended in the curable composition, and a color filter formed from the photosensitive polymer composition A light sheet and an image display element comprising the color filter.

<Curable (meth)acrylate polymer>

The first aspect of the invention is a curable (meth) acrylate polymer. The polymer is characterized by having a repeating unit having a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton.

The repeating unit having the structure of an alicyclic skeleton and a direct bond of at least two carboxyl groups may be any repeating unit as long as at least two carboxyl groups are directly bonded to the alicyclic skeleton. Since the structure in which the alicyclic skeleton is directly bonded to the carboxyl group is obtained, a particularly excellent effect can be obtained in terms of availability of the raw material and yellowing resistance of the cured product. The number of carboxyl groups bonded to the alicyclic skeleton is not limited, and for example, the number of 2, 3, 4, 5, and 6 may be selected. Head.

The curable (meth) acrylate polymer of the present invention having such a repeating unit is exemplified by a hydroxyl group as a raw material (meth) acrylate polymer having a monomer unit having a hydroxyl group, and has an alicyclic ring. A polymer obtained by subjecting an acid anhydride skeleton to a compound of a carboxyl group by an addition reaction. In the present specification, "(meth) acrylate" means one or both of acrylate and methacrylate.

First, a raw material (meth) acrylate polymer (hereinafter referred to as "precursor") containing a monomer unit having a hydroxyl group will be described below.

<(meth)acrylate polymer (precursor) as a raw material>

The (meth) acrylate polymer (precursor) used as a raw material used for the synthesis of the (meth) acrylate polymer of the present invention contains a monomer unit having a hydroxyl group as described above. As an example of a method of obtaining a precursor containing such a monomer unit, for example, the following three methods can be mentioned.

(first method)

In the first method, a (meth) acrylate monomer (a) having a hydroxyl group is used, and other ethylene having a structure which does not contain at least two carboxyl groups directly bonded to the alicyclic skeleton is used as needed. The radically polymerizable monomer (d) having a carbon-carbon double bond (hereinafter referred to as "other radical polymerizable monomer (d)") is a method of performing radical (co)polymerization in accordance with a general method.

Specific examples of the (meth) acrylate monomer (a) having a hydroxyl group are not particularly limited. For example, hydroxyethyl (meth)acrylate, 1,4-cyclohexane Dimethanol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Among these, in view of availability or reactivity, it is particularly preferred to use hydroxyethyl (meth)acrylate.

These monomers (a) may be used singly or in combination of two or more.

The radical polymerizable monomer (d) which can be used in combination as needed is a radical polymerizable property of an ethylenic carbon-carbon double bond having a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton. Monomers are not subject to any special restrictions and can be used as needed. For example, when the monomer (d-1) having no aromatic ring is used as the monomer (d), a curable polymer excellent in dispersibility of the dye can be obtained. Further, when a monomer (d-2) having an aromatic ring is used, a curable polymer excellent in dispersibility of the pigment can be obtained. These monomers may be used singly or in combination. In general, even when a photosensitive material exhibiting good performance in a pigment dispersion method is applied to a dye dispersion method, there are cases where sufficient performance is not necessarily exhibited or a pattern of the opposite is generated. However, in the present invention, by using a monomer (d-1) having no aromatic ring and a monomer (d-2) having an aromatic ring as needed, regardless of the dispersion method described above, good display performance can be obtained. a hardening polymer. At this time, the use ratio of the monomer (d-1) and the monomer (d-2) can be selected as needed, but in general, the molar ratio of (d-1)/(d-2) is 1/10~ 5/1, preferably 1/5~2/1, more preferably 1/3~1/1.

The other radical polymerizable monomer (d) is as follows.

(second method)

a second method for preparing a monomer unit having an epoxy group in a side chain The (meth) acrylate polymer is a method of ring-opening the epoxy group by subjecting a polymer having a carboxyl group, preferably (meth)acrylic acid, to the polymer. (In the present specification, "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid. Further, "side chain" means a moiety branched from a carbon atom constituting a main chain, and the main chain system a (meth) acrylate polymer having a monomer unit having an epoxy group in a side chain, which is formed by a carbon-carbon single bond formed by polymerization of an ethylene carbon-carbon double bond of the monomer, The (meth) acrylate monomer (b) having an epoxy group is used, and if necessary, another radical polymerizable monomer (d) is used in combination, and a method of radical (co)polymerization is carried out in accordance with a general method.

The above (meth) acrylate monomer (b) having an epoxy group can be arbitrarily selected. Specific examples thereof include glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, and 3,4-epoxy (meth)acrylate having an alicyclic epoxy group. Cyclohexylmethyl ester, and its lactone adduct (for example, Cyclomer (registered trademark) A200, M100 manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl-3', 4'-ring Mono(meth)acrylate of oxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth)acrylate, and epoxide of dicyclopentenyloxyethyl (meth)acrylate Wait. Among them, in terms of availability or reactivity, it is particularly preferred to use glycidyl (meth)acrylate. These monomers (b) may be used singly or in combination of two or more. The monomer unit having an epoxy group in the side chain in the (meth) acrylate polymer is derived from the (meth) acrylate monomer (b) having such an epoxy group.

In the second method, the other radical polymerizable monomer (d) which can be used in combination as desired can be used as described in the first method. The radically polymerizable monomer having an ethylene carbon-carbon double bond having a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton is equivalent. The details are as follows.

In the second method, the amount of the compound having a carboxyl group can be appropriately selected depending on the value of the hydroxyl group equivalent of the (meth) acrylate polymer (precursor) as a raw material. In general, the epoxy group contained in the polymer having the (meth) acrylate monomer unit having an epoxy group is 0.90 to 1 mol, preferably 0.95 to 1 mol per 1 mol. ear. When the amount used is in the above range, side reactions are not caused in the subsequent reaction, and it is preferred.

The conditions of the above reaction can be selected as needed, and can be carried out in accordance with a general method. For example, the above two components may be added to the reaction solvent, and a catalyst may be further added. For example, the reaction may be carried out at 50 to 150 ° C, preferably at 80 to 130 ° C for 3 to 12 hours. Further, in this reaction, there is no particular problem even if the solvent used in the copolymerization reaction is contained. Therefore, after the completion of the copolymerization reaction, the solvent can be removed without removing the solvent.

Moreover, in order to prevent gelation as needed, it is preferable to add a polymerization inhibitor. The type of the polymerization inhibitor is not particularly limited and is selected as needed. For example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, etc. are mentioned.

The type of the above-mentioned catalyst is not particularly limited and is selected as needed. For example, a tertiary amine such as triethylamine, a tertiary ammonium salt such as triethylbenzylammonium chloride, a phosphorus compound such as triphenylphosphine, a chromium compounding compound, and the like can be given.

(third method)

In a third method, in order to prepare a (meth) acrylate polymer having a monomer unit having a carboxyl group in a side chain, an epoxy group is opened by an addition reaction of a compound having an epoxy group . The (meth) acrylate polymer having a monomer unit having a carboxyl group in a side chain can be arbitrarily selected, for example, by using a (meth) acrylate monomer (c) having a carboxyl group, and if necessary, a combination of other The radically polymerizable monomer (d) is obtained by a method of radical (co)polymerization in accordance with a general method.

The (meth) acrylate monomer (c) having a carboxyl group can be arbitrarily selected. Specific examples thereof include (meth)acrylic acid, α-bromo (meth)acrylic acid, β-furyl (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, and Malay. An unsaturated carboxylic acid such as monomethyl ester, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate or monoethyl iconate. Among these, (meth)acrylic acid is particularly preferably used. These monomers (c) may be used singly or in combination of two or more. The monomer unit having a carboxyl group in the side chain in the (meth) acrylate polymer is derived from the (meth) acrylate monomer (c) having such a carboxyl group.

The compound having an epoxy group can be arbitrarily selected. Specific examples thereof include glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, and 3,4-epoxy (meth)acrylate having an alicyclic epoxy group. Cyclohexyl methyl ester, and its lactone adduct (for example, Cyclomer (registered trademark) A200, M100 manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl-3', 4'- Mono(meth)acrylate of epoxycyclohexanecarboxylate, epoxide of dicyclopentenyl (meth)acrylate, and dicyclopentanyl (meth)acrylate An epoxide of an allyloxyethyl group or the like. Among them, in terms of availability or reactivity, it is particularly preferred to use glycidyl (meth)acrylate. These compounds may be used singly or in combination of two or more.

In the third method, the other radical polymerizable monomer (d) which can be used in combination as needed is an ethylenic structure having a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton without being bonded to the alicyclic skeleton as described in the first method. The radically polymerizable monomer having a carbon-carbon double bond is equivalent, and will be described later.

By reacting the obtained polymer having a (meth) acrylate monomer unit having a carboxyl group, a compound having an epoxy group is subjected to an addition reaction, and the epoxy group is opened, and as a result, a hydroxyl group-containing compound is obtained. A (meth) acrylate polymer (precursor) as a raw material of a monomer unit. The amount of the compound having an epoxy group can be appropriately selected depending on the target value of the hydroxyl group equivalent of the (meth) acrylate polymer (precursor) as a raw material. In general, it is 0.05 to 0.8 mol, preferably 0.1 to 0.7 mol, based on the carboxyl group 1 mole contained in the polymer having a (meth) acrylate monomer unit having a carboxyl group. When the amount of the compound having an epoxy group is 0.05 mol or more, the unsaturated group equivalent does not become excessively large, and as a result, the performance of sensitivity or solvent resistance is not lowered, and it is preferable.

This reaction can be carried out under the same conditions as those described in the second method. For example, it is preferred to add two components to the reaction solvent, and further add a catalyst, for example, at 50 to 150 ° C, preferably 80 to 130 ° C. Further, in this reaction, there is no particular problem even if the solvent used in the copolymerization reaction is contained. Therefore, after the completion of the copolymerization reaction, the solvent can be removed without removing the solvent.

(Other radical polymerizable monomer (d))

In the above first to third methods, in addition to the monomer component, other ethylene carbon-carbons other than the repeating unit having a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton may be used in combination as needed. The radically polymerizable monomer (d) having a double bond, as described above, is a radical polymerizable property of an ethylenic carbon-carbon double bond having a structure in which at least two carboxyl groups are directly bonded to an alicyclic skeleton. Monomers are not particularly limited.

Specific preferred examples thereof include a polymerizable monomer having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms. The bridged cyclic hydrocarbon means a structure represented by the following formula (1) or (2) represented by adamantane, norbornane or the like. By bridged cyclic hydrocarbon group is meant a group equivalent to the portion remaining from the removal of a portion of the hydrogen atoms of such structures.

(In the formula (1), A ¹ and B ¹ each represent a linear or branched alkyl group (which may include a ring), and R ⁴ represents a hydrogen atom or a methyl group. A ¹ and B ¹ may be the same or may be Differently, the branches of A ¹ and B ¹ may be connected to each other to form a ring shape).

(In the formula (2), A ² , B ² and L each represent a linear or branched alkyl group (may also contain a ring), and R ⁵ represents a hydrogen atom or a methyl group. A ² , B ² , and L may be The same or different, the branches of A ² , B ² , and L may be connected to each other to form a ring shape.

Among the monomers having the above structure, a (meth) acrylate having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms is particularly preferable. Among these, a (meth) acrylate of (meth) acrylate or a (meth) acrylate having a structure represented by the following formula (3) is more preferable.

(In the formula (3), R ⁶ to R ⁸ each independently represent a hydrogen atom or a methyl group. R ⁹ and R ¹⁰ are a hydrogen atom or a methyl group, or may be bonded to each other to form a saturated or unsaturated ring, and the ring is preferably. It is a 5-membered ring or a 6-membered ring. In the formula, * represents a bonding site bonded to a (meth) acryloxy group.

Examples of the polymerizable monomer include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isodecyl (meth)acrylate, and adamantyl (meth)acrylate. . Among these, decomposition by heat From the viewpoints of properties, heat discoloration resistance, and the like, dicyclopentanyl methacrylate is particularly preferable. These monomers may be used alone or in combination of two or more.

Further, examples of the norbornene monomer represented by the following formula (4) are preferred monomers (d).

In the formula (4), X and Y each independently represent a hydrogen atom or a hydrocarbon group having a straight or branched chain of 1 to 4 carbon atoms, and R ¹ and R ² each independently represent a hydrogen atom, a carboxyl group or may have a hydrocarbon group having 1 to 20 carbon atoms in the substituent. R ¹ and R ² may also form a linked cyclic structure.

When X and Y are a hydrocarbon group of a linear or branched chain having 1 to 4 carbon atoms, specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and t. - butyl. Further, when R ¹ and R ² are a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, examples of R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. a straight or branched alkyl group such as isobutyl, t-butyl, t-pentyl, stearyl, lauryl or 2-ethylhexyl; an aryl group such as phenyl; cyclohexyl, t- An alicyclic group such as a butylcyclohexyl group, a dicyclopentadienyl group, a tricyclodecanyl group, an isodecyl group, an adamantyl group or a 2-methyl-2-adamantyl group. Specific examples of the substituent include an alkoxy group such as a methoxy group or an ethoxy group; an aryl group such as a phenyl group; and the like.

Examples of the above-mentioned norbornene monomer include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[ 2.2.1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]Dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]癸-8-ene, tricyclo[5.2.1.0 ^2,6 ]non-3-ene, tricyclo[4.4.0.1 ^2,5 ]und-3-ene, tricyclo[6.2.1.0 ^1,8 ] 1--9-ene, tricyclo[6.2.1.0 ^1,8 ]und-4-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, 8-ethylenetetracycline [4.4.0.1 ^2,5 .1 ^7,12 ]Dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ]dodec-3-ene, pentacyclic [6.5.1.1 ^3,6 . 0 ^2,7 .0 ^9,13 ] fifteen-4-ene, pentacyclic [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] fifteen-3-ene and the like. Among these, from the viewpoints of heat decomposition resistance, heat discoloration resistance, and the like, it is preferable that norbornene and dicyclopentadiene are used. These may be used alone or in combination of two or more.

Specific examples of the other radically polymerizable monomer (d) which can be used in combination include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, and the like. O-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p - an aromatic vinyl compound such as cyanostyrene or p-acetylamino styrene; a diene compound such as butadiene, isoprene or chloroprene; (meth)acrylic acid; Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylate Butyl ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate Ester, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol Mono (meth) acrylate, rosin (meth) acrylate, decyl (meth) acrylate, 5-methyl decyl (meth) acrylate, 5-ethyl decyl (meth) acrylate , (meth)acrylic acid tetrahydrofuran methyl ester, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, ( Perfluoro-isopropyl ester of methyl)acrylic acid, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate , cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth) acrylate, hydrazine Phenoxypolyethylene glycol mono(meth)acrylate, diphenoxyethyl (meth)acrylate, naphthalene (meth) acrylate, hydrazine (meth) acrylate, (meth) acrylonitrile Oxyethyl isocyanate (ie 2-isocyanatoethyl (meth)acrylate) and ε-caprolactam a (meth) acrylate compound such as a reaction product of (meth)acryloxyethyl isocyanate and propylene glycol monomethyl ether; (meth)acrylic acid decylamine or (meth)acrylic acid N, N-dimethylamine, N,N-diethylammonium (meth)acrylate, N,N-dipropylamine (meth)acrylate, N,N-diisopropylamine (meth)acrylate (meth)acrylamide such as (meth)acrylic acid decylamine; aniline (meth)acrylate, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, partial a vinyl compound of difluoroethylene, N-vinylpyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene or the like; An unsaturated dicarboxylic acid diester compound such as diethyl citrate, diethyl maleate, diethyl fumarate or diethyl itaconate; N-phenyl maleimide, N- A monomaleimide compound such as cyclohexylmaleimide, N-lauryl maleimide, N-(4-hydroxyphenyl)maleimide or the like.

These compounds (d) may be used alone or in combination of two or more. The amount or ratio of such combinations can also be selected as desired.

Among these, in particular, those having no nitrogen atom in the molecule can be preferably used from the viewpoint of yellowing resistance. In particular, when the polymerizable monomer having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms is used in a ratio of 15 to 70 mol% in the polymer, heat decomposition resistance and heat discoloration resistance are improved. Preferably.

(the ratio of monomers)

In the production of a (meth) acrylate polymer (precursor) containing a monomer unit having a hydroxyl group as a raw material, the (meth) acrylate monomer (a) having a hydroxyl group used in the first method and other freedoms The ratio of the base polymerizable monomer (d) can be selected as needed. It is preferred that the ratio of the (meth) acrylate monomer (a) having a hydroxyl group is 10 to 50 mol%, more preferably 15 to 40 mol%, and still more, relative to the total amount of the above monomers. Good for 20~35 moles.

Further, the ratio of the (meth) acrylate monomer (b) or (c) used in the second method and the third method to the other radical polymerizable monomer (d) may be selected as needed. Preferably, each (meth) acrylate monomer (b) or (c) is 30 to 90 mol%, more preferably 35 to 80 mol%, and still more preferably 40 to 75. Moer%.

The proportion of the other radical polymerizable monomer (d) can be arbitrarily selected, for example, 10 to 70 mol%, preferably 20 to 65 mol%, more preferably 25 to 60 mol%.

In the first method, when the (meth) acrylate monomer (a) having a hydroxyl group is at least 10 mol% or more, it is easy to introduce a desired amount of the side chain of the polymer to bond directly to the alicyclic skeleton at least 2 The structure of the carboxyl group is preferred. Moreover, when it is 50 mol% or less, the solvent resistance is sufficient, and it is preferable.

In the second method and the third method, when the (meth) acrylate monomer (b) or (c) is 30 mol% or more, it is easy to introduce a desired amount of a hydroxyl group into a side chain of the polymer, and preferably, In particular, when the (meth) acrylate monomer (b-1) is used, it is preferred to introduce a desired amount of a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton. On the other hand, when it is 90 mol% or less, the adhesiveness and the dispersibility with a dye or a pigment become sufficient, and it is preferable.

In the production of a (meth) acrylate polymer (precursor) as a raw material in a monomer unit having a hydroxyl group in a side chain, the other radical polymerizable monomer (d) is not essential. However, heat resistance and pigment dispersibility can be suitably improved by using the monomer of (d) in combination as needed. In particular, a polymerizable monomer having a bridged cyclic hydrocarbon group having 7 to 20 carbon atoms is used in combination, and as the other radical polymerizable monomer (d), heat resistance and yellowing resistance are improved. Therefore, it is preferred to use these monomers in an appropriate amount.

For (meth) acrylate monomer (a) having a hydroxyl group, (meth) acrylate monomer (b) having an epoxy group, (meth) propyl having a carboxyl group The conditions of the copolymerization reaction of the enoate monomer (c) and other radical polymerizable monomer (d) to be used may be arbitrarily selected. For example, the reaction can be carried out in the presence or absence of a polymerization solvent in accordance with a radical polymerization method well known in the art. For example, after dissolving these monomers in a solvent selected as needed, a polymerization initiator is added to the solution, and polymerization is carried out at 50 to 130 ° C for 1 to 20 hours.

Further, the (meth) acrylate monomer (a) having a hydroxyl group, the (meth) acrylate monomer (b) having an epoxy group, and the (meth) acrylate monomer having a carboxyl group (c) Further, the other radical polymerizable monomer (d) to be used as needed may be used in combination as needed, as long as it contains any of the monomers (a) to (c). For example, the monomer (a) and the monomer (b) may be combined and produced by combining the monomer (a) and the monomer (c), or may be used by combining the monomers (a) to (c). The ratio can be arbitrarily chosen.

(solvent)

The solvent to be used in the copolymerization reaction is not particularly limited and may be selected as needed. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, Diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, two (poly)alkylene glycol monoalkyl group such as propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Ether compound; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol (poly)alkylene glycol monoalkyl ether acetate compound such as monomethyl ether acetate, propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Other ether compounds such as ether, diethylene glycol diethyl ether, tetrahydrofuran; ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, Ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, acetic acid 3-methyl-3-methoxybutyl ester, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, N-butyl acetate, i-butyl acetate, n-pentyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, Butyl n-butyl ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutyrate, etc. An ester compound; an aromatic hydrocarbon compound such as toluene or xylene; a carboxylic acid amide compound such as N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide Wait. These solvents may be used alone or in combination of two or more.

Among these, (poly)alkylene glycol monoalkyl ether solvent such as propylene glycol monomethyl ether, and (poly)alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate The solvent, that is, the glycol ether solvent is preferred.

The amount of the solvent used for the polymerization is not particularly limited and may be selected as needed. As an example, when the total amount of monomer feed is 100 mass In the case of a portion, it is usually 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass. When the amount of the solvent used is 1,000 parts by mass or less, the molecular weight reduction of the copolymer due to chain transfer can be efficiently suppressed, and the viscosity of the copolymer can be controlled to an appropriate range. In addition, when the amount of the solvent blended is 30 parts by mass or more, the polymerization reaction can be prevented from being abnormal, and the polymerization reaction can be carried out stably. Further, it is also possible to prevent the color or gelation of the copolymer.

(polymerization initiator)

The polymerization initiator which can be used in the copolymerization reaction is not particularly limited and may be selected as needed. For example, azobisisobutyronitrile, azobisisovaleronitrile, benzammonium peroxide, and t-butylperoxy-2-ethylhexanoate may, for example, be mentioned. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator to be used can be arbitrarily selected. In a preferred embodiment, when the total amount of the monomer is 100 parts by mass, it is generally 0.5 to 20 parts by mass, preferably 0.7 to 15 parts by mass, more preferably 1 to 10 parts by mass.

(a compound having an alicyclic anhydride skeleton and a carboxyl group)

The (meth) acrylate polymer (precursor) as a raw material containing a monomer unit having a hydroxyl group prepared as described above, and a compound having an alicyclic acid anhydride skeleton and a carboxyl group, may be formulated and have an alicyclic ring A monoester of a compound of an acid anhydride skeleton and a carboxyl group as a monomer unit of the curable (meth) acrylate polymer of the present invention.

Further, in the case of using a compound having an acid anhydride skeleton of an aromatic ring, transparency may be obtained if a compound having an alicyclic acid anhydride skeleton is used. Excellent tendency.

The aforementioned compound having an alicyclic acid anhydride skeleton and a carboxyl group can be selected as needed. As an example, the alicyclic skeleton is preferably a cycloalkane skeleton having 5 to 8 carbon atoms or a bridged ring skeleton having 7 to 11 carbon atoms; more preferably, the alicyclic anhydride skeleton is further Further, the carboxycyclic skeleton is a cyclohexane skeleton, a cycloheptane skeleton, or a bicyclo[3,2,0]heptane skeleton. For example, 1,2,4-cyclohexanetricarboxylic anhydride represented by the following formula (5), 1,2,4-cyclopentanetricarboxylic anhydride represented by the following formula (6), and 3-oxygen Heterobicyclo[3,2,0]heptane-6-carboxylic acid, 7,7-dimethyl-2,4-dioxy (CAS: 1378785-58-0), and the like. Among these, in terms of reactivity and ease of availability, it is particularly preferred to be 1,2,4-cyclohexanetricarboxylic anhydride. In addition, examples of the compound having an alicyclic acid anhydride skeleton and a carboxyl group are examples in which the carboxyl group is one. However, the number of carboxyl groups is not particularly limited, and may be one or more. For example, the number of carboxyl groups of the above compound may be 2, 3, 4 or 5 or the like.

By the above reaction, for example, when the 1,2,4-cyclohexanetricarboxylic anhydride represented by the formula (5) is reacted with a hydroxyl group of a (meth)acrylate polymer as a raw material, the structural system represented by the following formula Incorporation into a hardenable (meth) acrylate polymer. When 1,2,4-cyclopentanetricarboxylic anhydride is used, a structure in which a hexane skeleton of the following formula is changed to a heptane skeleton is incorporated.

(Preferred physical properties of (meth)acrylate polymer (precursor) as a raw material)

The physical properties of the (meth) acrylate polymer as a raw material can be selected as desired, but it is preferred to have the following characteristics. The weight average molecular weight obtained by gel permeation chromatography in terms of polystyrene is preferably 800 to 48,000, more preferably 2,000 to 38,000. The preferred range is preferably 2000 to 30,000, or 2000 to 20,000, depending on the desired effect or condition. When the weight average molecular weight is 800 or more, when a photosensitive polymer composition is used, it is preferable that no defect of a coloring pattern occurs after alkali development. When the molecular weight is 48,000 or less, the development time is an appropriate period of time, and it is preferable to use it in practical use.

The (meth) acrylate polymer used in the present invention is preferably linear polymerization. The material may have a chain, a branch, or a crosslinked structure as needed, or may have a mesh structure.

Any polymer may be used as long as it is within the scope of the invention, and may be a random copolymer, an interactive copolymer, a block copolymer or a graft copolymer. The first to third methods described above may be combined as needed to produce a (meth) acrylate polymer as a raw material.

(conditions of addition reaction)

The reaction of a (meth) acrylate polymer (precursor) containing a monomer unit having a hydroxyl group as a raw material, and a compound having an alicyclic acid anhydride skeleton and a carboxyl group can be arbitrarily selected, and can be carried out, for example, in accordance with a general method. For example, the reaction can be carried out by adding a polymerization inhibitor and a catalyst by adding two components to the reaction solvent, for example, at 50 to 150 ° C, preferably at 80 to 130 ° C for 1 to 10 hours.

The amount of the compound having an alicyclic acid anhydride skeleton and a carboxyl group used in the reaction can be appropriately selected in accordance with the value of the hydroxyl equivalent of the target curable (meth) acrylate polymer. In general, the amount of use of the hydroxyl group 1 mol contained in the raw material (meth) acrylate polymer (precursor) containing a monomer unit having a hydroxyl group is 0.1 to 0.8 mol, preferably 0.2. ~0.7 moles. When the amount used is too large, there is a possibility of side reactions, and therefore it is preferably used in an appropriate amount.

The polymerization inhibiting agent and the catalyst used for the reaction may be similarly used in the preparation of a raw material (meth) acrylate polymer (precursor) containing a monomer unit having the above-mentioned hydroxyl group.

(physical properties of hardenable (meth) acrylate polymer)

The curable (meth) acrylate polymer of the present invention has a weight average molecular weight obtained by gel permeation chromatography in terms of polystyrene, preferably from 1,000 to 50,000, more preferably from 3,000 to 40,000, still more preferably 5,000~20,000, especially 6,000~10,000.

When the weight average molecular weight is 1,000 or more, when a photosensitive polymer composition is used, it is preferable that no defect of a coloring pattern occurs after alkali development. When the molecular weight is 50,000 or less, the development time becomes an appropriate period of time, and it is preferable to use it in practical use.

The acid value (JIS K6901 5.3) of the curable (meth) acrylate polymer of the present invention can be appropriately selected. When it is used as a photosensitive polymer, it is generally in the range of 10 to 300 KOHmg/g, preferably 20 to 250 KOHmg/g. When the acid value is 10 KOHmg/g or more, sufficient alkali developability as a photosensitive polymer can be obtained, and it is preferable. On the other hand, when the acid value is 300 KOHmg/g or less, the exposed portion (photohardened portion) is not dissolved in the alkali developing solution, and as a result, an excellent pattern shape is obtained.

The hydroxyl value of the aforementioned polymer (JIS K0070) can be selected as needed. Generally, it is in the range of 70 to 300 KOHmg/g, preferably 85 to 250 KOHmg/g. When the valence of the hydroxyl group is 70 KOHmg/g or more, the adhesion or developability are sufficient, and it is preferable. On the other hand, when the valence of the hydroxyl group is 300 KOHmg/g or less, the solvent resistance is sufficient, and it is preferable.

The unsaturated group equivalent of the above polymer is not particularly limited and may be arbitrarily selected. Generally, it is preferably from 100 to 4,000 g/mol, preferably It is in the range of 200 to 2,000 g/mol, more preferably 300 to 500 g/mol. When the unsaturated group equivalent is 100 g/mol or more, it is preferable in terms of improving the physical properties of the coating film and alkali developability. On the other hand, when the unsaturated group equivalent is 4,000 g/mol or less, it is effective in improving the sensitivity. Furthermore, the aforementioned unsaturated bond equivalent means the mass of the polymer per 1 mol of the unsaturated bond of the polymer. This value can be determined by dividing the mass of the polymer by the amount of unsaturated bonds of the polymer (g/mol). In the present specification, "unsaturated bond equivalent" is a theoretical value calculated from the amount of the raw material used to introduce the unsaturated bond.

(Example of a monomer unit of a curable (meth) acrylate polymer)

The curable (meth) acrylate polymer of the present invention may have various monomer units derived from the monomer or compound used. Some of the preferred examples of these are described below.

<Sclerosing composition>

Next, a preferred example of the curable composition containing the curable (meth) acrylate polymer of the second aspect of the present invention will be described.

The curable composition of the present invention may contain, in addition to the above-described first aspect of the present invention, a curable (meth) acrylate polymer (component A, hereinafter referred to as A), which may contain an optional component, for example. A solvent (component B, hereinafter referred to as B), a reactive diluent (component C, hereinafter referred to as C), a photopolymerization initiator (component D, hereinafter referred to as D), and a color former (hereinafter referred to as D) At least one of the E component (hereinafter referred to as E) is used as a curable composition.

(solvent (B))

The solvent (B) is not particularly limited as long as it is a solvent which dissolves the curable polymer (A) and is compatible with the reactive diluent (C) described later and does not react with the curable polymer (A). Can be chosen at will. For example, the same solvent as that which can be used in the production of the aforementioned curable (meth) acrylate polymer (A) can be used. Specific examples thereof include the aforementioned examples. Preferably, a (poly)alkane monoalkyl ether solvent such as propylene glycol monomethyl ether or a (poly)alkane monoalkyl ether acetate solvent such as propylene glycol monomethyl ether acetate is used. That is, a glycol ether solvent.

The curable composition of the present invention may be prepared by appropriately mixing the desired solvent (B) from the target mixture of the curable (meth) acrylate polymer (A). However, in order to get this The curable composition of the invention does not necessarily have to be isolated from the curable (meth) acrylate polymer (A) in the polymerization system. The solvent contained in the end of the copolymerization reaction may be separated from the polymer (A) and left as it is, and it may be used as a composition of the present invention. Further, other desired solvents may be further added to the above composition as needed. Further, the solvent contained in the other components used in the preparation of the curable composition may be used and/or added as a component of the solvent (B).

(Reactive diluent (C))

The reactive diluent (C) (polymerizable monomer) is a compound having at least one polymerizable ethylenically unsaturated group in the molecule as a polymerizable functional group. Among them, a plurality of polymerizable functional groups are particularly preferred. Such a reactive diluent is not necessarily an essential component of the curable composition. However, by using this in combination with the curable (meth)acrylate polymer (A), the film strength of the coating film formed from the above composition or the adhesion to the substrate can be improved.

The monofunctional monomer used as the reactive diluent can be arbitrarily selected. For example, (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, C Oxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate Ester, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (methyl) ) 2-phenoxy-2-hydroxypropyl acrylate Ester, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofuran methyl (meth)acrylate, glycidyl (meth)acrylate , 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, half (meth) acrylate of phthalic acid derivatives, etc. (meth) acrylate compound; aromatic vinyl compound such as styrene, α-methyl styrene, α-chloromethyl styrene, vinyl toluene; carboxylic acid such as vinyl acetate or vinyl propionate Ester and the like. Further, these may be used alone or in combination of two or more.

The polyfunctional monomer used as the reactive diluent can be arbitrarily selected. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol can be mentioned. Di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylol Propane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol Methyl)acrylate, 2,2-bis(4-(methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxypolyethoxylate Phenyl phenyl) propane, 2-hydroxy-3-(methyl) propylene methoxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl Ether di(meth) acrylate, diglycidyl di(meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth) acrylate, urethane (A Base) Ester (i.e., toluene diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene a (meth) acrylate compound such as a reaction product of methyl diisocyanate with 2-hydroxyethyl (meth) acrylate or a tri(meth) acrylate of hydroxy(hydroxyethyl) trimer isocyanate; An aromatic vinyl compound such as benzene, diallyl phthalate or diallyl phenylphosphonate; a dicarboxylate compound such as divinyl adipate; triallyl isocyanurate Methylene bis(meth) acrylamide, (meth) acrylamide dimethyl ether, a condensate of a polyol and N- hydroxymethyl (meth) acrylamide, and the like. Further, these may be used alone or in combination of two or more.

The blending amount of the polymer (A), the solvent (B) and the reactive diluent (C) in the curable composition may be appropriately selected depending on the purpose of use. In general, when the total of the component (A) and the component (C) is 100 parts by mass, the curable polymer (A) is 10 to 100 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, and the reaction is diluted. The agent (C) is 0 to 90 parts by mass. It is preferably 20 to 80 parts by mass of the curable polymer (A), 50 to 800 parts by mass of the solvent (B), and 20 to 80 parts by mass of the reactive diluent (C). More preferably, it is 30 to 75 parts by mass of the polymer (A), 100 to 700 parts by mass of the solvent (B), and 25 to 70 parts by mass of the reactive diluent (C). When the blending amount is within this range, a curable composition having a suitable viscosity can be obtained, and it can be preferably used in order to prepare a photosensitive polymer composition to be described later. Further, it can be preferably used as various coatings, adhesives, binders for printing inks, and the like.

<Photosensitive polymer composition>

Next, a photosensitive polymer composition containing a curable (meth) acrylate polymer in a preferred embodiment of the above composition of the present invention will be described.

The photosensitive polymer composition of the present invention preferably contains a curable (meth) acrylate polymer (A), a solvent (B), and a photopolymerization initiator (component D, hereinafter referred to as D). .

The above composition may preferably contain a reactive diluent (C) and/or a coloring agent (component E, hereinafter referred to as E) as needed.

As the curable (meth) acrylate polymer (A), the solvent (B), and the reactive diluent (C), it is also preferred to use a curable composition containing the aforementioned curable (meth) acrylate polymer. The same is contained in the same.

(Photopolymerization initiator (D))

The photopolymerization initiator (D) is not particularly limited and can be arbitrarily selected. For example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[4- (Methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1, etc. Acetophenone compound; anthraquinone compound such as 2-methylindole, 2-pentylindole, 2-t-butylindole, 1-chloroindole; xanthone, thioxanthone (thioxanthone), 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like xanthone compounds; acetophenone dimethyl ketal, benzyl a ketal compound such as dimethyl ketal; benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3', 4,4 a benzophenone compound such as --(t-butyldioxycarbonyl)benzophenone; a mercaptophosphine oxide compound. These may be used alone or in combination of two or more.

The blending amount of the photopolymerization initiator (D) in the photosensitive polymer composition can be arbitrarily selected, but when the total of the components (A) and (C) is 100 parts by mass, it is generally 0.1 to 30. The mass portion is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass. If it is blended in this range, a photosensitive polymer composition having suitable photocurability can be obtained.

(colorant (E))

The colorant (E) is not particularly limited as long as it is dissolved or dispersed in the solvent (B), and can be arbitrarily selected. For example, a dye, a pigment, etc. are mentioned. The dye preferably has a carboxylic acid, a sulfonic acid or the like from the viewpoints of solubility in the solvent (B) or the alkali developing solution, interaction with other components in the photosensitive polymer composition, and heat resistance. The acid-based acid dye, the salt of the nitrogen compound of the acid dye, and the sulfonamide of an acid dye are selected and used.

Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80 , 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; foodyellow3 and derivatives thereof. Among these, an acid dye such as an azo-based, xanthene, lanthanum or phthalocyanine system is preferred. These may be used alone or in combination of two or more depending on the color of the target pixel.

Examples of the pigments include CIPigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128. Yellow pigments of 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; CIPigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, Orange pigments of 61, 64, 65, 71, 73, etc.; CIPigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, Red pigments of 242, 254, 255, 264, 265, etc.; blue pigments of CIPigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; CIPigment Violet 1, 19, 23, 29, 32, 36 , purple pigments such as 38; green pigments such as CIPigment Green 7, 36, 58; brown pigments such as CIPigment Brown 23, 25; black pigments such as CIPigment Black 1, 7, carbon black, titanium black, iron oxide, and the like.

These dyes or pigments may be used alone or in combination of two or more depending on the color of the target color filter. Furthermore, the above dyes and pigments can be combined with each other depending on the color of the target color filter. use.

The blending amount of the colorant (E) can be arbitrarily selected. When the total of the components (A) and (C) is 100 parts by mass, it is usually 5 to 80 parts by mass, preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass.

When a pigment is used as the coloring agent (E), a known dispersing agent may be blended in the photosensitive polymer composition from the viewpoint of improving the dispersibility of the pigment. As the dispersing agent, a polymer dispersing agent excellent in dispersion stability over time is preferably used. The polymer dispersant can be arbitrarily selected, and examples thereof include a urethane dispersant, a polyethylenimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, and a sorbitan fat. A group ester dispersant, an aliphatic modified ester dispersant, and the like. As such a polymer dispersing agent, EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, BYK), Disparlon (registered trademark, manufactured by Nanben Chemical Co., Ltd.), SOLSPERS (registered trademark, A trade name of a product such as Zeneca Co., Ltd.). The blending amount of the dispersing agent may be appropriately set depending on the type of the pigment or the like to be used.

When the photosensitive polymer composition contains the coloring agent (E), the blending amount of each component is arbitrarily selected as needed. When the composition contains a curable (meth) acrylate polymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D), and a color former (E), this The blending amount of the above is preferably the following. In general, when the total amount of the component (A) and the component (C) in the photosensitive polymer composition is 100 parts by mass, the curable (meth) acrylate polymer (A) is 10 to 90% by mass. The solvent (B) is 30 to 1,000 parts by mass, the reactive diluent (C) is 10 to 90 parts by mass, and the photopolymerization initiator is used. (D) is 0.1 to 30 parts by mass, and the coloring agent (E) is 5 to 80 parts by mass. Preferably, the curable (meth) acrylate polymer (A) is 20 to 80 parts by mass, the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, and photopolymerization is carried out. The initiator (D) is 0.5 to 20 parts by mass, and the coloring agent (E) is 5 to 70 parts by mass. More preferably, the curable (meth) acrylate polymer (A) is 30 to 75 parts by mass, the solvent (B) is 100 to 700 parts by mass, the reactive diluent (C) is 25 to 70 parts by mass, and photopolymerization is carried out. The initiator (D) is 1 to 15 parts by mass, and the coloring agent (E) is 10 to 60 parts by mass. Further, when the photosensitive polymer composition does not contain the colorant (E), the curable (meth) acrylate polymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization start The above numerical range can also be preferably used for the blending amount of the agent (D).

The curable composition and the photosensitive polymer composition of the present invention may be blended with a known additive such as a known coupling agent, a leveling agent, and a thermal polymerization inhibiting agent in order to impart specific characteristics. The blending amount of such additives is not particularly limited as long as it does not inhibit the effects of the present invention.

The photosensitive polymer composition of the present invention can be produced by any method selected.

For example, it can be produced by mixing the above components by using a known mixing device. Further, first, a curable composition containing a curable (meth) acrylate polymer (A) and a solvent (B) may be first prepared, and then a reactive diluent (C) and a photopolymerization initiator may be further added. (D) and a coloring agent (E) of an optional component are produced by mixing.

The photosensitive polymer composition of the present invention is preferably used As a photoresist used for various purposes. It is particularly suitable as a photoresist used for the production of color filters in organic EL displays, liquid crystal display devices, and solid-state imaging devices such as CCDs and CMOSs. Further, the photosensitive polymer composition of the present invention imparts a cured film excellent in heat resistance, solvent resistance, dispersibility of a dye or pigment, and the like. Therefore, it can also be preferably used for various coatings, adhesives, adhesives for printing inks, and the like.

<Color Filter>

Next, a preferred example of the color filter of the third aspect of the present invention will be described.

The color filter of the present invention has a color pattern formed using the above-mentioned photosensitive polymer composition. The color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed on the boundary of each pixel, and a protective film formed on the pixel and the black matrix. In the above configuration, the pixels and the black matrix (coloring pattern) are formed by using the photosensitive polymer composition of the present invention described above, and other configurations can be employed.

Next, a preferred example of the method of manufacturing the color filter will be described.

First, a color pattern is formed on the substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited. For example, a glass substrate, a tantalum substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, or the like can be suitably used.

The coloring pattern can be formed by photolithography. in particular, It can be obtained as follows. First, the photosensitive polymer composition is applied onto a substrate to form a coating film. Thereafter, the coating film is exposed through a mask of a specific pattern to photoharden the exposed portion. The unexposed portion was then developed with an aqueous alkali solution and then baked. This forms a specific pattern.

The coating method of the photosensitive polymer composition is not particularly limited and can be arbitrarily selected. For example, a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like can be used. Further, after the application of the photosensitive polymer composition, it may be heated by a heating means such as a circulating oven, an infrared heater, or a heating plate as needed, whereby the solvent (B) contained in the coating film is volatilized. . The heating conditions are not particularly limited, and may be appropriately set depending on the type of the photosensitive polymer composition to be used. Generally, it is preferably heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.

Next, partial exposure is performed by irradiating the formed coating film with a negative mask to irradiate an active energy ray such as ultraviolet rays or excimer laser light. The amount of energy rays to be irradiated may be appropriately selected depending on the composition of the photosensitive polymer composition. For example, it is preferably 30 to 2,000 mJ/cm ² , but is not limited to this range. The light source used for the exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, and a metal halide lamp can be arbitrarily selected.

The aqueous alkali solution used for development is not particularly limited and may be optionally selected. For example, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide or the like; ethylamine, diethylamine, dimethylethanolamine can be used; An aqueous solution of an amine compound; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β- Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β An aqueous solution of a p-phenylenediamine compound such as a methoxyethyl aniline or a sulfate, a hydrochloride or a p-toluenesulfonate. Further, an antifoaming agent or a surfactant may be added to these aqueous solutions as needed. Further, after development with the above aqueous alkali solution, it is preferably washed with water and dried.

The hardening of the photosensitive polymer can be terminated by baking the pattern formed by alkali development after baking. The baking conditions are not particularly limited and may be arbitrarily selected. The heat treatment may be selected under the preferred conditions depending on the type of the photosensitive polymer composition to be used. For example, it is preferably used at a temperature of 130 ° C to 250 ° C for 10 minutes to 4 hours; more preferably for 20 minutes to 2 hours. However, it is not limited to these conditions.

By using the photosensitive polymer composition for the black matrix and the photosensitive polymer composition for red, green, and blue pixels, the steps of coating, exposure, development, and baking are sequentially repeated to form the substrate. The desired color pattern. Further, heretofore, a method of forming a color pattern by photocuring using a composition of the photopolymerization initiator (D) has been described, but the present invention is not limited to such methods. For example, when a composition in which a curing accelerator and a known epoxy resin are blended is used instead of the photopolymerization initiator (D), it may be heated by an inkjet method to be hardened. And the desired color pattern is formed.

Next, a protective film is formed on the coloring pattern (each pixel of RGB and the black matrix). The protective film is not particularly limited as long as it is formed by using a known person. Just fine.

The color filter manufactured in this manner has a high luminance because it is produced by using a photosensitive polymer composition of a color pattern which is excellent in sensitivity, developability, solvent resistance, and dispersibility of a dye or a pigment. The color pattern.

<Video display component>

An image display element according to a fourth aspect of the present invention is a display element having the above color filter. Specific examples thereof include liquid crystal display elements, organic EL display elements, solid-state imaging elements such as CCD elements and CMOS elements, and the like. When the image display element is manufactured, there is no limitation other than the use of the color filter described above, and it can be manufactured in accordance with a general method. For example, when a liquid crystal display element is manufactured, the color filter is formed on a substrate, and then an electrode, a spacer, or the like is sequentially formed. Then, an electrode or the like is formed on the other substrate, and both of them are bonded together, and a specific amount of liquid crystal is injected and sealed.

[Examples]

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the embodiments. Furthermore, the invention is not limited to the embodiments. In the following examples, the parts and percentages are recorded, and unless otherwise specified, they are all based on the quality.

(Example 1)

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 93.3 g of propylene glycol monomethyl ether acetate as a solvent was added, and the inside of the flask was stirred with nitrogen while stirring, and the temperature was raised to 120 °C.

Next, it was prepared separately from 44.0 g (0.2 mol) of tricyclodecyl methacrylate, 26.0 g (0.2 mol) of 2-hydroxyethyl methacrylate, 17.2 g (0.2 mol) of methacrylic acid, and methyl group. To the monomer mixture of 70.4 g (0.4 mol) of benzyl acrylate, 14.2 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl (registered) was added. Trademark) O). The monomer/polymerization initiator mixture was dropped from the dropping funnel into the aforementioned flask for 2 hours. After completion of the dropwise addition, the mixture was further stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to form an addition copolymer (curable polymer precursor). Thereafter, the flask was replaced with air, and 29.7 g (0.15 mol) of cyclohexane-1,2,4-tricarboxylic anhydride and 0.6 g of triphenylphosphine (catalyst) were charged into the above-mentioned addition copolymer solution. . Thereafter, the reaction was continued at 110 ° C for 10 hours to react a hydroxyl group in the polymer with an acid anhydride, and a carboxyl group was introduced into the side chain. As a result, a (meth) acrylate polymer (sample 1) represented by the formula (20) was obtained. The polymer had an acid value of 140 KOHmg/g and a weight average molecular weight of 8,400. In the formula, a, b, c, d and e represent the number of monomer units, and are an integer of 1 or more.

Next, 353.1 g of propylene glycol monomethyl ether was added to the reaction solution to prepare a polymer solution having a solid concentration of 35% of the curable polymer (A). For the evaluation of Sample 1, the solution was used for various evaluations shown below.

(Example 2)

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 124.4 g of propylene glycol monomethyl ether acetate as a solvent was added, and the inside of the flask was stirred with nitrogen while stirring, and the temperature was raised to 120 °C.

Next, it was prepared separately from 33.0 g (0.15 mol) of tricyclodecyl methacrylate, 31.4 g (0.15 mol) of styrene, and 99.4 g (0.7 mol) of glycidyl methacrylate. 9.5 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl (registered trademark) O) was added to the mixture.

The monomer/polymerization initiator mixture was dropped from the dropping funnel to the front 2 hours in the flask. After completion of the dropwise addition, the mixture was further stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to form an addition copolymer (curable polymer precursor). Thereafter, the inside of the flask was replaced with air, and 49.0 g (0.7 mol) of acrylic acid, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of BHT (polymerization inhibiting agent) were placed in the above-mentioned addition copolymer solution. Thereafter, the reaction was continued at 110 ° C for 10 hours, and the epoxy group in the polymer was reacted with acrylic acid to introduce a polymerizable unsaturated bond. Next, 39.6 g (0.2 mol) of cyclohexane-1,2,4-tricarboxylic anhydride was added to the reaction system, and the reaction was continued at 110 ° C for 3 hours to form a hydroxyl group formed by the cracking of the epoxy group and four. The anhydride group of hydrogen phthalic anhydride reacts to introduce a carboxyl group into the side chain. As a result, a curable (meth) acrylate polymer represented by the formula (21) (sample 2) was obtained. The polymer had an acid value of 100 KOHmg/g and a weight average molecular weight of 9,400. In the formula, f, g, h and i represent the number of monomer units, and are an integer of 1 or more. In the same manner as in Example 1, a polymer solution having a solid concentration of 35% of the obtained polymer was prepared.

(Example 3)

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 124.4 g of propylene glycol monomethyl ether acetate as a solvent was added, and the inside of the flask was stirred with nitrogen while stirring, and the temperature was raised to 120 °C.

Next, it was additionally prepared by adding 33.0 g (0.15 mol) of tricyclodecyl methacrylate, 31.4 g (0.15 mol) of styrene, and 60.2 g (0.7 mol) of methacrylic acid. 9.5 g of t-butylperoxy-2-ethyl hexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbutyl (registered trademark) O). The monomer/polymerization initiator mixture was dropped from the dropping funnel into the aforementioned flask for 2 hours.

After completion of the dropwise addition, the mixture was further stirred at 120 ° C for 2 hours to carry out a copolymerization reaction to form an addition copolymer (curable polymer precursor). Thereafter, the flask was replaced with air, and 99.4 g (0.7 mol) of glycidyl methacrylate, 0.6 g of triphenylphosphine (catalyst), and 0.6 g of BHT (polymerization inhibitor) were added to the above addition copolymerization. In the solution. Thereafter, the reaction was continued at 110 ° C for 10 hours, and the epoxy group in the polymer was reacted with acrylic acid to introduce a polymerizable unsaturated bond. Next, 39.6 g (0.2 mol) of cyclohexane-1,2,4-tricarboxylic anhydride was added to the reaction system, and the reaction was continued at 110 ° C for 3 hours to form a hydroxyl group formed by the cracking of the epoxy group and four. The anhydride group of hydrogen phthalic anhydride reacts to introduce a carboxyl group into the side chain. The curable (meth) acrylate polymer (sample 3) represented by the obtained formula (22) had an acid value of 90 KOH mg/g and a weight average molecular weight of 10,000. In the formula, j, k, l and m represent the number of monomer units, and are an integer of 1 or more. In the same manner as in Example 1, a polymer solution having a solid concentration of 35% of the obtained polymer was prepared.

(Examples 4 to 6 and Comparative Examples 1 to 3)

Thereafter, Examples 4 to 6 and Comparative Examples 1 to 3 were synthesized in the same manner as in Examples 1 to 3, and the samples 4 to 9 were obtained in the same manner as shown in the following Table.

(Measurement method of physical property value)

The acid value, the unsaturated group equivalent, the hydroxyl value, and the weight average molecular weight described in the examples are values obtained by the methods described below.

(1) Acid value: The acid value of the curable (meth) acrylate polymer measured in accordance with JIS K6901 5.3. The number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the curable (meth) acrylate polymer.

(2) Unsaturated group equivalent: The mass of the polymer per unit mole of the polymerizable unsaturated bond, which is a calculated value based on the amount of use of the monomer.

(3) Hydroxyl value: hydroxyl group of the curable polymer measured in accordance with JIS K0070 price. It means the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of the above-mentioned curable polymer is acetylated.

(4) Weight average molecular weight (Mw): means a weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) under the following conditions.

Pipe column: Shodex (registered trademark) LF-804+LF-804 (made by Showa Denko Co., Ltd.)

Column temperature: 40 ° C

Sample: 0.2% tetrahydrofuran solution of copolymer

Developing solvent: tetrahydrofuran

Detector: Differential Refractometer (Shodex (registered trademark) RI-71S) (made by Showa Denko Co., Ltd.)

Flow rate: 1mL/min

(Examples 7 to 12, and Comparative Examples 4 to 6)

Samples 1 to 9 prepared using Examples 1 to 6 and Comparative Examples 1 to 3, The transparent photosensitive polymer compositions (transparent photoresists) of Examples 7 to 12 and Comparative Examples 4 to 6 were prepared by the following blending.

In addition, the number No. 1 - No. 9 of the photosensitive polymer composition correspond to the sample number (No. 1 - No. 9) used. In the above description of the blending, the mass of the samples 1 to 9 does not include the solvent used for the preparation of the polymer solution. The amount of the solvent contained in the polymer solution is calculated by combining the above-mentioned solvents as the doping component.

<Evaluation of Transparent Light Resistance>

The adhesion and heat-resistant yellowing were evaluated by the method shown below. The results are shown in Table 2.

Evaluation of adhesion:

The prepared transparent photoresist was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness of the final cured coating film became 2.5 μm. Thereafter, the solvent was volatilized by heating at 90 ° C for 3 minutes. Next, the entire surface of the coating film was exposed (exposure amount: 50 mJ/cm ² ), and photocuring was performed. Thereafter, the film was baked at 230 ° C for further 30 minutes to obtain a target cured film. The coating film was subjected to a checkerboard test in accordance with JIS K5400. Specifically, the peeling state of 100 checkers was visually observed, and the adhesion was evaluated by the following criteria.

◎ (Excellent): Peeling was not observed at all.

○ (good): Peeling was observed in 1 to 2% of the whole.

△ (may): Peeling was observed in 3 to 9% of the whole.

× (not available): Peeling was observed at 10% or more of the whole.

Evaluation of heat-resistant yellowing:

A coating film obtained by using the above-mentioned photoresist film was prepared on a glass substrate, and the coating film was allowed to stand in a dryer at 230 ° C for 1 hour. The light transmittance at 400 nm was measured by a spectrophotometer on the coating film before and after the heat treatment. The heat-resistant yellowing was evaluated using the obtained light transmittance and the following criteria.

◎ (Excellent): The rate of change of transmittance is 0.5% or less.

○ (good): The rate of change in transmittance is 0.7% or less.

△ (may): The rate of change of the transmittance is 1% or less.

× (not available): The rate of change in transmittance is 1% or more.

The results are shown in Table 2. From the results shown in Table 2, it is understood that the transparent resist of the present invention of Examples 7 to 12 is excellent in heat-resistant yellowing and adhesion, and a transparent photoresist having a radical polymerizable group is introduced (No. 2 and 3). ), with more excellent heat-resistant yellowing. On the other hand, the photoresists of Comparative Examples 4 to 6 were inferior, and in particular, the use of tetrahydrophthalic anhydride as the addition anhydride in Comparative Examples 5 and 6 was low in heat-resistant yellowing and the adhesion was not sufficient. Minute.

(Examples 13 to 18, and Comparative Examples 7 to 9)

<Preparation of photosensitive polymer composition (dye type)>

Using the samples 1 to 9 prepared in Examples 1 to 6 and Comparative Examples 1 to 3, photosensitive polymerization of the dyes (acid green 3) of Examples 13 to 18 and Comparative Examples 7 to 9 was prepared by the following blending. Composition (color resist (dye type)).

In addition, the numbers (No. 1 to No. 9) of the photosensitive polymer composition described in Table 2 correspond to the sample numbers (No. 1 to No. 9) of the polymer to be used. . Further, the mass of the samples 1 to 9 described in the following blending does not include the solvent used for the preparation of the polymer solution. The amount of the solvent contained in the above polymer solution is calculated by combining the following solvents as the doping component.

<Evaluation of color photoresist (dye type)>

The alkali developability, sensitivity, and solvent resistance of the photosensitive polymer compositions of Examples 13 to 18 and Comparative Examples 7 to 9 were evaluated by the methods shown below. The results are shown in Table 2.

(1) Forming a pattern with colored photoresist

The prepared color resist (dye type) was spin-coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure became 2.5 μm to form a coating film. Thereafter, the solvent was volatilized by heating at 90 ° C for 3 minutes. Next, a mask of a specific pattern was placed at a distance of 100 μm from the coating film, and the coating film was exposed through the mask (exposure amount: 150 mJ/cm ² ) to photo-curing the exposed portion. Next, the aqueous solution containing 0.1% by mass of sodium carbonate was sprayed at a temperature of 23 ° C and a pressure of 0.2 MPa to dissolve the unexposed portion for development. Thereafter, by baking at 230 ° C for 30 minutes, a specific pattern for evaluation including a line pattern of different sizes was formed.

(2) Evaluation of patterns formed by colored photoresists

With respect to the pattern formed as described above, alkali developability, sensitivity, and adhesion were evaluated by the following methods.

(2-1) Alkali developability

The alkali developability was confirmed by evaluation of the residue of the unexposed portion after alkali development and the development form of the pattern. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High Technologies.

The basis for this assessment is as follows.

○ (good): no residue

× (not available): there is residue

(2-2) Sensitivity

The amount of reduction in the thickness of the pattern before and after the development of the alkali obtained by the alkali development (30 seconds) using the above spray was measured. By the amount of reduction, it is determined whether the sensitivity is good or not. The thickness of the pattern, the less the amount of reduction, the better the sensitivity. Therefore, the basis for this assessment is as follows.

○ (good): The thickness reduction of the pattern is less than 0.15 μm.

△ (may): The thickness reduction of the pattern is 0.15 μm or more and less than 0.20 μm.

× (not available): The thickness reduction of the pattern is 0.20 μm or more.

(2-3) Adhesion

The width of the minimum line pattern in which the pattern was formed was observed with an optical microscope, and the adhesion after baking was evaluated by the following criteria. Furthermore, the better the adhesion, the more the micropattern can be formed.

◎ (Excellent): The width of the smallest pattern is less than 5 μm.

○ (good): The width of the minimum pattern is less than 10 μm and is 5 μm or more.

× (not available): The width of the minimum pattern is 10 μm or more.

(3) Evaluation of solvent resistance

On the 5cm square glass substrate (alkali-free glass substrate), the above color The photoresist was spin-coated so that the thickness after exposure became 2.5 μm. Thereafter, the obtained coating film was heated at 90 ° C for 3 minutes to evaporate the solvent. Next, the coating film was exposed to light having a wavelength of 365 nm, and the exposed portion was subjected to photocuring. Thereafter, it was allowed to stand in a drier having a baking temperature of 230 ° C for 30 minutes to prepare a cured coating film. 200 mL of N-methyl-2-pyrrolidone was placed in a 500 mL-capped glass vial, and a test piece with the above-mentioned hardened coating film was immersed therein. Then, after passing for 1 hour at 23 ° C, the color change of the coating film of the test piece was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Evaluation of solvent resistance was performed based on the results. The basis for this assessment is as follows.

◎(Excellent): △E ^* ab is less than 0.2

○ (good): △E ^* ab is 0.2 or more and less than 0.25

△ (may): △E ^* ab is 0.25 or more and less than 0.3

× (not available): ΔE ^* ab is 0.3 or more

As is clear from the results of Table 2, the color resists (using the photosensitive polymer compositions No. 1 to 6) of Examples 13 to 18 using the photosensitive polymer composition (dye type) of the present invention were used for alkali developability. , sensitivity, solvent resistance and adhesion show good performance. On the other hand, the color resist of the photosensitive polymer composition No. 7 of Comparative Example 7 was used, and the solvent resistance and the adhesion were poor as compared with those of the photosensitive polymer compositions No. 1 to 6. . The results of Comparative Examples 8 and 9 were not satisfactory, but excellent results were not obtained.

(Examples 19 to 24, and Comparative Examples 10 to 12)

<Preparation of photosensitive polymer composition (pigment type)>

In a stainless steel container filled with 180 parts of zirconia beads having a diameter of 0.5 mm, 10 parts of CI Pigment Green 36, 33.75 parts of propylene glycol monomethyl ether acetate, and a dispersing agent (Disperbyk, BYK. Japan Co., Ltd.) were charged. (registered trademark) - 161) 6.25 copies. The mixture was dispersed in a paint shaker for 3 hours to disperse, thereby preparing a green pigment dispersion.

Using the green pigment dispersion liquid, a photosensitive polymer composition (pigment type) containing a green pigment was prepared by blending the samples 1 to 9 or less. In addition, the number (No. 1 - No. 9) of the photosensitive polymer composition corresponds to the sample number (No. 1 - No. 9) used. Further, the mass of the samples 1 to 9 described in the following blending does not include the solvent used for the preparation of the polymer solution. The amounts of the foregoing solvents are combined and calculated in the solvent as a doping component.

<Evaluation of color resist (pigment type)>

The above photosensitive polymer composition was evaluated by the method shown below The pigment dispersion.

The alkali developability, sensitivity, adhesion, and solvent resistance of the photosensitive polymer composition were carried out in the same manner as the evaluation of the dye type. The results are shown in Table 2.

Evaluation of pigment dispersion:

In the above blending, a green resin composition was prepared in the same manner except that the photopolymerization initiator was not contained. The viscosity after standing for 7 days in the thermostat at 40 ° C was measured by an E-type viscometer. The rate of change was calculated and the quality of the pigment dispersion was evaluated by the following criteria.

◎ (Excellent: very good dispersion): The viscosity change rate is less than 15%.

○ (good: good dispersibility): The viscosity change rate was 15% or more and less than 20%.

△ (may: slightly less dispersibility): The viscosity change rate is 20% or more and less than 25%.

× (not: poor dispersion): The viscosity change rate is 25% or more.

As is clear from the results of Table 2, the color resists (using photosensitive polymer compositions No. 1 to 6) of the photosensitive polymer composition (pigment type) of Examples 19 to 24 of the present invention were used for alkali developability. Good performance in terms of sensitivity, solvent resistance, pigment dispersibility, and adhesion. On the other hand, the color resists of Comparative Examples 10 to 12 (using photosensitive polymer compositions No. 7 to 9) using the photosensitive polymer compositions of Comparative Examples 1 to 3 were used for pigment dispersibility and solvent resistance. None of the sex and adhesion is bad.

(Examples 25 to 30, and Comparative Examples 13 to 15)

<Preparation of photosensitive polymer composition (mixed type of dye/pigment)>

In a stainless steel container filled with 180 parts of zirconia beads having a diameter of 0.5 mm, 10 parts of CI Pigment Green 36, 33.75 parts of propylene glycol monomethyl ether acetate, and a dispersing agent (Disperbyk, BYK. Japan Co., Ltd.) were charged. (registered trademark) - 161) 6.25 copies. The mixture was dispersed in a paint shaker for 3 hours to disperse, thereby preparing a green pigment dispersion.

Using the green pigment dispersion liquid 40 parts and 2 parts of acid green 3, the photosensitive polymer composition (dye/pigment type) was prepared by the following mixing. In addition, the number (No. 1 - No. 9) of the photosensitive polymer composition corresponds to the sample number (No. 1 - No. 9) used. Further, among the amounts of the samples 1 to 9 (polymer) described below, the solvent used for the preparation of the polymer solution was not included. The amount of the solvent contained in each polymer solution was calculated and calculated in the following solvent as a blending component.

<Evaluation of photosensitive polymer composition (mixed type of dye/pigment)>

The above-mentioned photosensitive polymer composition was used as a color resist (dye/pigment mixed type), and its performance was evaluated in the same manner as a color resist (pigment type). The results are shown in Table 2.

As is clear from the results of Table 2, the color resists (using the photosensitive polymer compositions No. 1 to 6) of the photosensitive polymer composition (dye/pigment type) of Examples 25 to 30 of the present invention were used, and the base was used. Good performance is exhibited in developability, sensitivity, solvent resistance, pigment dispersibility, and adhesion. On the other hand, the color resists of Comparative Examples 13 to 15 (using the photosensitive polymer compositions No. 7 to 9) were inferior in performance.

From the results of the above examples and comparative examples, it was confirmed that the polymer of the present invention exhibits an excellent effect, and the composition or color resist obtained from the above polymer also exhibits excellent characteristics.

[Industrial availability]

According to the present invention, it is possible to obtain a curable polymer which is excellent in sensitivity, developability, solvent resistance as a cured product, adhesion to a substrate, and dispersibility of a coloring agent when used as a photosensitive material. Moreover, the cured coating film formed from the photosensitive polymer composition of the present invention is excellent in solvent resistance, adhesion to a substrate, and dispersibility of a coloring agent. Accordingly, the use value in various photoresist fields is extremely high. Among these, in particular, when used as a photosensitive material for a color filter, a color filter type color filter having solvent resistance, adhesion to a substrate, and dispersibility of a coloring agent can be obtained.

According to the present invention, a curable polymer which is excellent in sensitivity, developability, heat-resistant yellowing property as a cured product, solvent resistance, adhesion to a substrate, and dispersibility of a coloring agent, and photosensitive property of the above-mentioned curable polymer are provided. A polymer composition; a color filter formed using the aforementioned photosensitive polymer composition.

Claims (16)

A curable (meth) acrylate polymer characterized by comprising a repeating unit having a structure in which at least two carboxyl groups are directly bonded to an alicyclic skeleton. The curable (meth) acrylate polymer of claim 1, wherein the alicyclic skeleton is selected from a naphthenic skeleton having 5 to 8 carbon atoms and a bridged ring skeleton having 7 to 11 carbon atoms. At least one of them. The curable (meth) acrylate polymer according to claim 1 or 2, wherein the alicyclic skeleton is a cyclohexane skeleton, a cycloheptane skeleton, and a bicyclo[3,2,0]heptane skeleton. Choose at least one of them. The sclerosing (meth) acrylate polymer according to any one of claims 1 to 3, wherein the aforementioned repeating unit having a structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton is (meth)acrylic acid. The side chain of the ester polymer has a repeating unit of a hydroxyl group and a monoester of a compound having an alicyclic acid anhydride skeleton and a carboxyl group. The sclerosing (meth) acrylate polymer of claim 4, wherein the side chain in the (meth) acrylate polymer has a repeating unit of a hydroxyl group, and the compound having an epoxy group is added to the side chain. A repeating unit having a repeating unit of a carboxyl group. The sclerosing (meth) acrylate polymer according to claim 4, wherein the above-mentioned repeating unit having a hydroxyl group in a side chain in the (meth) acrylate polymer has a ring in which a compound having a carboxyl group is added to a side chain. The repeating unit derived from the repeating unit of the oxy group. A sclerosing (meth) acrylate polymer according to any one of claims 1 to 6 The compound further contains a repeating unit derived from an ethylenic carbon-carbon double bond having no structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton. The sclerosing (meth) acrylate polymer of claim 7, wherein the aforementioned repeating unit derived from an ethylenic carbon-carbon double bond having no structure in which at least two carboxyl groups are directly bonded to the alicyclic skeleton is derived from: a (meth) acrylate monomer having a structure represented by the following formula (3) (In the formula (3), R ⁶ to R ⁸ each represent a hydrogen atom or a methyl group; R ⁹ and R ¹⁰ represent a hydrogen atom or a methyl group, or a saturated or unsaturated ring which is bonded to each other; wherein * represents a linkage to a (meth) propylene oxime bond site), a decene monomer represented by the following formula (4) (X and Y in the formula (4) each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms which may be linear or branched, and R ¹ and R ² each independently represent a hydrogen atom or a carboxyl group. Or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a repeating unit which may be a ring structure of R ¹ and R ² , a (meth)acrylic monomer, or a styrene monomer. . The sclerosing (meth) acrylate polymer according to any one of claims 1 to 8, wherein the above-mentioned repeating unit having an alicyclic skeleton and at least two carboxyl groups is represented by the formula (15) to the formula (19). At least one; The curable (meth) acrylate polymer according to any one of claims 1 to 9, which has a polystyrene-equivalent weight average molecular weight of from 1,000 to 50,000 as measured by gel permeation chromatography. A curable composition containing at least one of a curable (meth) acrylate polymer according to any one of claims 1 to 10, a solvent, a reactive diluent, a photopolymerization initiator, and a coloring agent. The hardenable composition of claim 11, wherein the colorant is at least one of a dye and a pigment. A color filter formed using the hardenable composition of claim 11 or 12. An image display device comprising a color filter as claimed in claim 13. A method for producing a curable (meth) acrylate polymer having an alicyclic skeleton in a side chain and at least two carboxyl groups directly bonded to the skeleton The method comprising: (i) a step of preparing a (meth) acrylate polymer having a hydroxyl group in a side chain, and (ii) a compound having an alicyclic acid anhydride skeleton and a carboxyl group, and having the aforementioned side chain The step of reacting a hydroxyl group of a hydroxyl (meth) acrylate polymer. The method for producing a curable (meth) acrylate polymer according to claim 15, wherein the step (i) comprises the steps of: (i-1) preparing a (meth)acrylic acid having a carboxyl group in a side chain; An ester polymer or a step of a (meth) acrylate polymer having an epoxy group in a side chain; and (i-2) a carboxyl group-addition epoxy compound or a carboxyl group added to the epoxy group A compound, which is formed in the step of forming a (meth) acrylate polymer having a hydroxyl group in a side chain.