KR101360816B1 - Alkali soluble resin, process for producing the same, photosensitive resin composition containing the same, cured product, and color filter - Google Patents

Abstract

Provided is an alkali-soluble resin that is excellent in the formation of a fine pattern and forms a photosensitive resin composition suitable for a material for high light shielding or fixed color filters.

It is represented by General formula (1) and is alkali-soluble resin which has a carboxylic acid residue and a polymerizable unsaturated group in a molecule | numerator.

(Wherein R ₁ to R ₄ are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, R ₅ is a hydrogen atom or a methyl group, X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -0-, 9,9-fluorenylene group or a direct bond, Y is a tetravalent carboxylic acid residue G is a substituent having a polymerizable double bond and a carboxyl group represented by the following general formula (2): Z is a substituent represented by the following general formula (3): n is 1 to 20)

(Wherein R ₈ is a C3-C6 aliphatic hydrocarbon group, R ₆ is a divalent alkylene group, R ₇ is a hydrogen atom or a methyl group, Z is the same as the following general formula (3), and q is 0 or 1)

(Wherein L is a divalent or trivalent carboxylic acid residue, p is 1 or 2)

Color filter, soluble resin, photosensitive resin composition, black matrix

Description

Alkali SOLUBLE RESIN, PROCESS FOR PRODUCING THE SAME, PHOTOSENSITIVE RESIN COMPOSITION CONTAINING THE SAME, CURED PRODUCT, AND COLOR FILTER}

This invention relates to alkali-soluble resin which can harden | cure by irradiating an ultraviolet-ray or an electron beam, and the pattern formation by alkali image development process, its manufacturing method, and the photosensitive resin composition using this alkali-soluble resin, and is specifically, for a color filter It is a photosensitive resin composition suitable for obtaining a resist, and relates to alkali-soluble resin suitable for forming this photosensitive resin composition.

The color liquid crystal display device includes a liquid crystal part for controlling the amount of light transmission or reflection and a curling filter. A method of manufacturing the color filter is generally performed by forming a black matrix on the surface of a transparent substrate such as glass or plastic sheet. A method of forming different colors of red, green, and blue into color patterns such as sequential, striped, or mosaic shapes is used. In recent years, color liquid crystal display devices have been used in all fields such as liquid crystal televisions, liquid crystal monitors, color liquid crystal mobile phones, and color filters are one of the important members that influence the visibility of these color liquid crystal display devices. The pattern size varies depending on the use of the color filter and the respective colors. The red, green, and blue pixels are thinned from 100 µm to 50 µm or less, and the black matrix is 20 µm to 10 µm or less. Therefore, pattern formation by high dimensional precision is calculated | required by the photosensitive resin composition.

Generally, the photosensitive resin composition in such a use uses the polyfunctional photocurable monomer which has a polymerizable unsaturated bond, alkali-soluble binder resin, and the composition which combined them and the photoinitiator. For example, Japanese Patent Application Laid-Open No. 61-213213 (Patent Document 1) or Japanese Patent Application Laid-Open No. Hei 1-52449 (Patent Document 2) exemplifies application as a color filter material, and as a binder resin. A copolymer of (meth) acrylic acid or (meth) acrylic acid ester having a carboxyl group with maleic anhydride and another polymerizable monomer is disclosed. However, since the copolymer disclosed herein is a random copolymer, distribution of alkali dissolution rate occurs in the light irradiation portion and in the light irradiation portion, and thus the margin at the time of developing operation is narrow and acute angle pattern It is difficult to obtain a fine pattern. In particular, when a pigment of high concentration is included, the exposure sensitivity is remarkably lowered, and a fine negative pattern cannot be obtained. In addition, Japanese Patent Application Laid-open No. Hei 4-340965 (Patent Document 3) discloses that an alkali-soluble unsaturated compound having a polymerizable unsaturated double bond and a carboxyl group in one molecule is effective for forming negative patterns such as color filters. It is. It is expected that the molecules having alkali solubility will be insoluble by light irradiation in comparison with the above-described combination of the binder resin and the polyfunctional polymerizable monomer, but the compound exemplified herein is polymerizable to the hydroxyl group of the phenol oligomer. Acrylic acid and an acid anhydride, which are unsaturated bonding groups, are optionally added. In the case of this proposal, the distribution of alkali dissolution rate is wide due to the nonuniformity of molecular composition, making it difficult to form a fine negative pattern.

On the other hand, Japanese Patent Application Laid-open No. Hei 4-345673 (Patent Document 4), Japanese Patent Application Laid-open No. Hei 4-345608 (Patent Document 5), Japanese Patent Application Laid-open No. Hei 4-355450 (Patent Document 6) and Japanese Patent Laid-Open No. 4-363311 (Patent Document 7) discloses a liquid resin using a reaction product of an epoxy (meth) acrylate having an bisphenol fluorene structure and an acid anhydride. However, the resins exemplified by these are small in molecular weight because they are reaction products of epoxy (meth) acrylates and acid anhydrides. Therefore, the sensitivity of a compound is low and a fine pattern cannot be formed.

Furthermore, dihydroxypropyl is disclosed in Japanese Unexamined Patent Publication No. Hei 5-339356 (Patent Document 8), Japanese Unexamined Patent Publication No. Hei 5-146132 (Patent Document 9), and WO94 / 00801 pamphlet (Patent Document 10). An alkali developable unsaturated resin composition by copolymerization of an acrylate compound and an acid dianhydride or an alkali developable unsaturated resin composition by copolymerization of an acid anhydride and an acid dianhydride with a dihydroxypropyl acrylate compound is disclosed. In this case, copolymerization of an acid dianhydride and a dihydroxypropyl acrylate compound proceeds to obtain an oligomer. However, since the number of polymerizable unsaturated bonds in a repeating unit is constant, the crosslinking density cannot be improved, and it is difficult to form a thin wire pattern under high concentration pigment, and there is room for improvement.

In addition, JP-A-9-325494 (Patent Document 11) increases the molecular weight of the carboxyl group-containing copolymer to polyfunctionalize the alkali-soluble resin composition. However, also in this case, since the number of polymerizable unsaturated bonds in a repeating unit is constant similarly to the above-mentioned patent document, improvement of a crosslinking density cannot be achieved.

[Patent Document 1] Japanese Patent Application Laid-Open No. 61-213213

[Patent Document 2] Japanese Unexamined Patent Publication No. Hei1-152449

[Patent Document 3] Japanese Unexamined Patent Publication No. Hei 4-340965

[Patent Document 4] Japanese Unexamined Patent Publication No. 4-345673

[Patent Document 5] Japanese Unexamined Patent Publication No. 4-345608

[Patent Document 6] Japanese Unexamined Patent Publication No. Hei 4-355450

[Patent Document 7] Japanese Unexamined Patent Publication No. Hei 4-363311

[Patent Document 8] Japanese Unexamined Patent Publication No. Hei 5-339356

[Patent Document 9] Japanese Unexamined Patent Publication No. Hei 5-146132

[Patent Document 10] Brochure of WO94 / 00801

[Patent Document 11] Japanese Patent Application Laid-Open No. 9-325494

Therefore, the inventors of the present invention have studied diligently to solve the problems in the conventional photosensitive resin composition. As a result, the present invention is polymerizable to a carboxyl group-containing copolymer obtained by reacting a diol compound containing a polymerizable unsaturated group with an acid dianhydride. It was discovered that an alkali-soluble resin suitable for formation of the photosensitive resin composition was obtained by reacting an epoxy compound containing an unsaturated bond group and further reacting an acid anhydride. By using this alkali-soluble resin, the crosslinking density is improved while controlling the solubility in the alkaline developer, so that the difference in solubility with respect to the alkali developer in the hardened part and the uncured part is increased, and the fine wire pattern can be formed cleanly. It succeeded in obtaining the photosensitive resin composition with a close adhesive margin.

Therefore, the objective of this invention is providing the photosensitive resin composition which is excellent in formation of a fine pattern, and is suitable as a material for high light shielding or fixed color filter, and alkali-soluble resin which forms this photosensitive resin composition.

Another object of the present invention is to provide a coating film (cured product) and a color filter formed by using the above high-sensitive photosensitive resin composition.

Further, another object of the present invention is to provide a photosensitive resin composition for black matrices which is excellent in the formation of fine patterns even when a high concentration of light-shielding pigment is added, and which is preferable as a black matrix material for high-shielding or fixed color filters.

That is, this invention is represented by following General formula (1), It is alkali-soluble resin characterized by having a carboxylic acid residue and a polymerizable unsaturated group in a molecule | numerator.

Provided that R ₁ , R ₂ , R _3, and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. X represents -CO -, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -0-, 9,9-fluorenyl A valent group or a direct bond, and Y represents a tetravalent carboxylic acid residue G represents a substituent having a polymerizable double bond and a carboxyl group represented by the following general formula (2): Z is represented by the following general formula (3) Substituent represents n, and n represents a number from 1 to 20.)

(Wherein R ₈ is a C3-C6 aliphatic hydrocarbon group, R ₆ is a divalent alkylene group, R ₇ is a hydrogen atom or a methyl group, Z is the same as the following General Formula (3), and q is 0 or 1) Indicates the number of.)

(Wherein L represents a divalent or trivalent carboxylic acid residue and p is 1 or 2).

Moreover, this invention is the photosensitive resin composition containing (i) said alkali-soluble resin, (ii) photopolymerizable monomer which has at least 1 or more ethylenically unsaturated bond, and (iii) photoinitiator as an essential component.

Moreover, this invention is a hardened | cured material obtained by hardening the said photosensitive resin composition, and is a color filter formed by the hardened | cured material obtained by apply | coating and hardening the said photosensitive resin composition.

Furthermore, the present invention contains at least one polymerizable double bond in a reactant having a carboxyl group obtained by reacting a diol compound (A) containing a polymerizable unsaturated group with an acid dianhydride (B), and simultaneously contains 1 oxirane ring. A reactant having a hydroxyl group is obtained by reacting a dog-containing oxirane compound (C), followed by reacting an acid anhydride (D) with a reactant having a hydroxyl group.

Moreover, this invention is represented by (i) following General formula (1), Alkali-soluble resin which has a carboxylic acid residue and a polymerizable unsaturated group in 1 molecule,

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -0-, 9,9-fluore A nylene group or a direct bond, Y represents a tetravalent carboxylic acid residue, G represents a substituent having a polymerizable double bond and a carboxyl group, Z represents a substituent represented by the following general formula (3), and n represents 1 The number of -20 is shown.

(Wherein L represents a divalent or trivalent carboxylic acid residue and p is 1 or 2).

(ii) photopolymerizable monomers having at least one ethylenically unsaturated bond

(iii) a photoinitiator, and

(iv) light-shielding pigments

It is a photosensitive resin composition for black matrices which contains as an essential component.

Since the photosensitive resin composition of this invention contains alkali-soluble resin represented by General formula (1), since the solubility to alkali developing solution is high compared with the conventional thing and there are many ethylenically unsaturated bond groups in 1 molecule, the crosslinking density after hardening Is high. That is, since the solubility difference with respect to the alkaline developing solution of the hardened part and the uncured part after ultraviolet ray or electron beam irradiation becomes large, a fine pattern can be formed also in thin film or a high colorant density | concentration. Therefore, the photosensitive resin composition of this invention is suitable for forming a color filter, and is especially preferable as a color filter protective film material and a material for black matrix formation. The color filter thus obtained is very useful, for example, in a transmissive, reflective or transflective color liquid crystal display device, a color image pickup device, a color sensor, and the like.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition (The photosensitive resin composition for black matrices is also included. The same is hereafter mentioned unless it mentions specially.) The alkali image development type photosensitive resin which contains alkali-soluble resin represented by General formula (1) as a main component. It is a resin composition which has a property as a composition. Since alkali-soluble resin represented by General formula (1) has a photopolymerizable unsaturated group derived from the diol compound which has (meth) acrylic acid, it not only has radical polymerizability but also contains acidic anhydride and acidic anhydride derived from acid dianhydride. Has alkali solubility.

Alkali-soluble resin of General formula (1) makes (meth) acrylic acid react with the epoxy compound which has two glycidyl ether groups derived from bisphenol, and tetracarboxylic acid is carried out to the diol compound (A) which has a polymerizable unsaturated group obtained. Or a carboxyl group obtained by reacting an acid dianhydride (B) thereof with the oxirane compound (C) containing a polymerizable double bond and reacting dicarboxylic acid or its acid anhydride (D) with the obtained reactant. It is an alternating copolymer. Since alkali-soluble resin of General formula (1) has a polymerizable unsaturated double bond and a carboxyl group, it provides outstanding photocurability, positive developability, and patterning property to alkali developing photosensitive resin composition, and provides a protective film, a light shielding film, It brings about the improvement of the physical properties of each pixel of red, green and blue.

The manufacturing method of alkali-soluble resin represented by General formula (1) is demonstrated in detail. First, alkali-soluble resin of General formula (1) reacts the epoxy compound which has two glycidyl ether groups derived from bisphenol, Especially preferably, the epoxy compound and (meth) acrylic acid represented by General formula (4) It is derived from the diol compound (A) containing the polymerizable unsaturated group obtained by making it.

In the above general formula (4), R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, preferably a hydrogen atom or 1 carbon atom. It is a -5 alkyl group or a phenyl group, More preferably, it is a hydrogen atom. X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -0-, 9 Although a 9- fluorenylene group or a direct bond is shown, it is preferable that it is a 9, 9- fluorenylene group. The 9,9-fluorenylene group refers to a group represented by the following general formula (5).

The reaction of such an epoxy compound and (meth) acrylic acid can use a well-known method, for example, using about 2 mol of (meth) acrylic acid with respect to 1 mol of epoxy compounds. The reactant obtained by this reaction is described in the said patent document 6 etc., for example. The reactant obtained by this reaction is a diol compound (A) containing a polymerizable unsaturated group, and is an epoxy (meth) acrylate compound represented by following General formula (6).

As a preferable bisphenol which gives alkali-soluble resin of General formula (1), the following are mentioned. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) Sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4 -Hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5 -Dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3 , 5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy -3,5-dichlorophenyl) ether and the like. Further, it is preferable that X is a 9,9-fluorenyl group such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy- (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, Fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9- Bis (4-hydroxy-3,5-dibromophenyl) fluorene, and the like. Furthermore, 4,4'-biphenol, 3,3'-biphenol etc. are mentioned preferably.

Alkali-soluble resin of General formula (1) can be obtained from the epoxy compound derived from the above-mentioned bisphenols, However, In addition to such epoxy compound, two glycidyl compounds, such as a phenol novolak-type epoxy compound and a cresol novolak-type epoxy compound, also exist. It can be used as long as it contains the compound which has an ether group significantly. When the bisphenols are glycidyl etherized, oligomer units represented by the following general formula (7) are incorporated, but the average value of m in the general formula (7) is 0 to 10, preferably 0 to If it is the range of 2, there is no problem in the performance of this resin composition.

Next, the main compound represented by General formula (1) by reaction of the diol compound containing a polymerizable unsaturated group, tetracarboxylic acid or its acid dianhydride, the oxirane compound containing a polymerizable unsaturated group, and dicarboxylic acid or its acid anhydride. The manufacturing method of alkali-soluble resin of this invention is demonstrated. An example of the manufacturing method of alkali-soluble resin of this invention is shown to following Reaction formula (I).

(However, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y and G are the same as in the general formula (1). R ₆ is a divalent alkylene group, R ₇ is a hydrogen atom. Or a methyl group, Z represents a substituent represented by the general formula (3), and n is a number from 1 to 20, p is the same as in the general formula (3), and q is 0 or 1 Number.)

Regarding the reaction formula (I), first, the epoxy (meth) acrylate compound of the general formula (6) obtained by the reaction of the above-described epoxy compound and (meth) acrylic acid [diol compound (A) containing a polymerizable unsaturated group) ] And an acid component are reacted, and the compound [reactant which has a carboxyl group] represented by General formula (8) is obtained. Although it does not restrict | limit especially about reaction conditions, such as a solvent and a catalyst used at this time, For example, it describes in the said patent document 11 etc. in detail. As the acid component, tetracarboxylic dianhydride (B) capable of reacting with a hydroxyl group in the epoxy (meth) acrylate compound molecule is preferably used. This acid component is effective in either saturated or unsaturated. Among these, as tetracarboxylic dianhydride (B), acid dianhydride of saturated linear hydrocarbon tetracarboxylic acid, acid dianhydride of alicyclic tetracarboxylic acid, acid dianhydride of aromatic tetracarboxylic acid, etc. can be used.

Here, examples of the acid dianhydride of saturated straight hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentane tetracarboxylic acid, acid dianhydride of hexanetetracarboxylic acid, and the saturated cyclic hydrocarbon substituted with saturated cyclic hydrocarbon. The acid dianhydride of tetracarboxylic acid may be sufficient.

Moreover, as an acid dianhydride of alicyclic tetracarboxylic acid, cyclobutane tetracarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane tetracarboxylic acid, cycloheptane tetracarboxylic acid, the acid dianhydride of norbornane tetracarboxylic acid, etc. are mentioned, Furthermore, the acid dianhydride of alicyclic tetracarboxylic acid substituted by saturated hydrocarbon may be sufficient. Examples of the acid dianhydride of aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, biphenylethertetracarboxylic acid, and acid dianhydrides of diphenylsulfontetracarboxylic acid. The acid dianhydride in the present invention is preferably an acid dianhydride of biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid and biphenylethertetracarboxylic acid, more preferably biphenyltetracarboxylic acid and biphenylethertetracarboxylic acid. Acid is an anhydride. These acid dianhydrides can also be used together 2 or more types.

It does not specifically limit about the method of manufacturing the compound represented by General formula (8) by making an epoxy (meth) acrylate compound and an acid component react, The well-known method like what was described in the said patent document 11 can be employ | adopted. Preferably, the molar ratio of the diol compound (A) and acid dianhydride (B) having a polymerizable unsaturated group represented by the general formula (6) so that the terminal of the compound represented by the general formula (8) becomes a hydroxyl group [(B) / (A)] is preferably quantitatively reacted to 50 mol% or more and less than 100 mol%. When the molar ratio is less than 50 mol%, the content of the unreacted epoxy (meth) acrylate compound increases, which may cause deterioration in aging stability of the alkali-soluble resin composition. On the other hand, when the molar ratio is 100 mol% or more, the terminal of the compound represented by the general formula (8) becomes an acid anhydride, and the content of unreacted acid dianhydride increases, which may cause side reactions when the oxirane compound is reacted later. . Moreover, as reaction temperature, it is preferable to add at 90-130 degreeC, to melt | dissolve a raw material uniformly, to carry out reaction, and to carry out reaction and aging at 40-80 degreeC continuously.

Next, an oxirane compound (C) is made to react with the compound represented by the said General formula (8), and the compound (reactant which has a hydroxyl group) represented by General formula (9) is obtained. The oxirane compound is a compound containing one or more polymerizable double bonds and at the same time one oxirane ring, and glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl Ether, 3,4-epoxycyclohexyl methacrylate, and the like.

It does not specifically limit about the manufacturing method of the compound represented by General formula (9), The general reaction conditions of addition reaction of carboxylic acid and an epoxy compound can be used. Moreover, the manufacturing method of the epoxy (meth) acrylate compound by reaction of the epoxy compound and the (meth) acrylic acid of patent document 11 mentioned above can also be referred to. As reaction temperature at the time of synthesize | combining the compound represented by General formula (9), the range of 40-120 degreeC is preferable, More preferably, it is 40-90 degreeC. The molar ratio of the oxirane compound (C) in synthesizing the compound represented by the general formula (9) is based on the acid dianhydride (B) used in the reaction of the compound represented by the general formula (8), that is, the molar ratio [ (C) / (B)] is preferably 160 to 220 mol%. When the molar ratio is less than 160 mol%, since the unreacted carboxylic acid is present, part of the ester bond derived from the acid dianhydride in the compound represented by the general formula (9) becomes half ester, and thus the molecular weight decreases due to the regeneration reaction of the acid anhydride. I am concerned. On the other hand, when molar ratio exceeds 220 mol%, the time-dependent change of alkali-soluble resin represented by General formula (1) by side reaction etc. derived from an unreacted oxirane compound is concerned.

Next, the hydroxyl group and acid anhydride (D) of the compound represented by General formula (9) are reacted, and alkali-soluble resin represented by General formula (10) is obtained. As the acid monoanhydride (D), an acid anhydride of saturated linear hydrocarbon dicarboxylic acid, an acid anhydride of saturated cyclic hydrocarbon dicarboxylic acid, an acid anhydride of aromatic dicarboxylic acid, and the like can be used. Among these, as an acid anhydride of saturated linear hydrocarbon dicarboxylic acid, for example, succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citrasalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimeline Anhydrides, such as an acid, a sebacic acid, a sumeric acid, and a diglycolic acid, are mentioned, Furthermore, the linear hydrocarbon dicarboxylic acid anhydride by which the hydrocarbon group was substituted may be sufficient. Moreover, as an acid anhydride of saturated cyclic hydrocarbon dicarboxylic acid, acid anhydrides, such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydro trimellitic acid, are mentioned, for example. Furthermore, the acid anhydride of alicyclic dicarboxylic acid substituted with saturated hydrocarbon may be sufficient. Moreover, as an acid anhydride of unsaturated dicarboxylic acid, the acid anhydride of maleic acid, itaconic acid, a phthalic acid, tetrahydrophthalic acid, methyl endo methylene tetrahydrophthalic acid, chloric acid, trimellitic acid is mentioned, for example. Among these, an acid anhydride (D) is preferably an anhydride of succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydro trimellitic acid, phthalic acid and trimellitic acid, and more preferably an acid anhydride of succinic acid, itaconic acid and tetrahydrophthal. to be. It is needless to say that the alkali-soluble resin represented by the general formula (10) is an example of the alkali-soluble resin represented by the general formula (1).

As reaction temperature at the time of reacting the hydroxyl group and acid-anhydride (D) of the compound represented by General formula (9), and synthesize | combining the compound represented by General formula (10), the range of 20-120 degreeC is preferable, and more Preferably it is 40-90 degreeC. The molar ratio of the acid monoanhydride (D) when synthesizing the compound represented by the general formula (10) is the number of moles of the diol compound (A), acid dianhydride (B) and oxirane compound (C) having the polymerizable unsaturated group ( molar ratio [(D) / {2 [(A)-(B) + (C)]}] to the formula (2 × ((A)-(B)) + (C)) converted from mol); Is preferably from 20 to 110 mol%. The molar ratio of an acid anhydride can be arbitrarily changed in the above-mentioned range for the purpose of adjusting the acid value of alkali-soluble resin represented by the said General formula (1).

An example of a method for producing the general formula (1) will be described below with reference to the case where 9,9-bis (hydroxyphenyl) fluorene is used as a starting material.

First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenol fluorene type epoxy compound represented by the following general formula (11), and the bisphenol fluorene type epoxy compound And (meth) acrylic acid represented by CH ₂ = CHR ₅ -COOH (R ₅ is the same as described above) to synthesize a bisphenol fluorene type epoxy (meth) acrylate resin represented by the following general formula (12). Subsequently, this bisphenol fluorene type epoxy (meth) acrylate resin is heated in a solvent such as propylene glycol monomethyl ether acetate, followed by acid dianhydride (B), oxirane compound (C) and acid anhydride (D). By reaction, alkali-soluble resin of the said General formula (1) is obtained.

Moreover, the photosensitive resin composition of this invention contains alkali-soluble resin of the said General formula (1) as a main component of a resin component. Here, the resin component means the component which becomes a resin by superposing | polymerizing or hardening, and contains an oligomer and a monomer other than resin. In addition, containing as a main component means that alkali-soluble resin of General formula (1) contains 30 weight% or more, Preferably it is 50 weight% or more, More preferably, 60 weight% or more is contained in a resin component. The photosensitive resin composition of this invention may contain alkali-soluble resin represented by General formula (1) as an essential component, and components other than resin of General formula (1) may be resin components, such as a solvent, a filler, a coloring agent, etc. A non-resin component may be sufficient.

In order to utilize the characteristics as a photosensitive resin composition, it is preferable to contain following (i)-(iii) component as an essential component. That is, (i) alkali-soluble resin represented by the said General formula (1), (ii) photopolymerizable monomer which has at least 1 or more ethylenically unsaturated bond, and (iii) photoinitiator are included as an essential component.

Moreover, the photosensitive resin composition for black matrices of this invention contains following (i), (ii), (iii) and (iv) component as an essential component. That is, (i) alkali-soluble resin which has a carboxylic acid group and a polymerizable unsaturated group in 1 molecule represented by General formula (1), (ii) photopolymerizable monomer which has at least 1 ethylenically unsaturated bond, (iii) photopolymerization Initiator, and (iv) light-shielding pigment.

Among these, as a photopolymerizable monomer which has at least 1 or more ethylenically unsaturated bond which is (ii) component, it is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethyl, for example. Monomers having hydroxyl groups such as hexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (Meth) (meth) acrylic acid esters such as acrylates. These compounds may be used alone or in combination.

About the compounding ratio [(i) / (ii)] of these (ii) component and (i) alkali-soluble resin represented by General formula (1), it is good that it is 20/80-90/10, Preferably it is 40 It is good that it is / 60-80 / 20. When the compounding ratio of alkali-soluble resin is small, the hardened | cured material after photocuring will fall, and since the acid value of a coating film is low in an unexposed part, the solubility to alkaline developing solution will fall, and the pattern edge will be uneven and it will not become sharp. Occurs. On the contrary, when the compounding ratio of alkali-soluble resin becomes larger than the said range, the ratio of the photoreactive functional group which occupies for resin is small, formation of crosslinked structure is not enough, and acid value in resin component is too high, Since the solubility with respect to alkaline developing solution becomes high, there exists a possibility that a problem may arise that the formed pattern becomes narrower than the target line | wire width, or a pattern falls easily.

As the photopolymerization initiator of component (iii), for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, and p- acetophenones such as tert-butylacetophenone, benzophenones such as benzophenone, 2-chlorobenzophenone, p, p ', and -bisdimethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin iso Benzoin ethers such as propyl ether and benzoin isobutyl ether, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m- Methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2, Nonimidazole compounds such as 4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p- Cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- halomethylthiazole compounds such as (p-methoxystyryl) -1,3,4-oxadiazole, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( 4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4 , 6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3, Halomethyl-s-triazine compounds such as 5-triazine and 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine; 1,2 -Octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o- Benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-jade o-acyl oxime compounds such as -o-acetate and 1- (4-methylsulfanylphenyl) butan-1-one oxime-o-acetate, benzyl dimethyl ketal, thioxanthone, 2-chloro thioxanthone, Sulfur compounds such as 2,4-diethyl thioxanthone, 2-methyl thioxanthone and 2-isopropyl thioxanthone, 2-ethyl anthraquinone, octamethyl anthraquinone, 1,2-benzanthraquinone, 2, Anthraquinones such as 3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, and 2-mercapto Thiol compounds such as benzothiazole, tertiary amines such as triethanolamine, triethylamine, and the like. These copolymerization initiators can use 1 type (s) or 2 or more types.

It is preferable that the usage-amount of the photoinitiator of (iii) component is 2-50 weight part based on a total of 100 weight part of (i) alkali-soluble resin represented by General formula (1) and (ii) photopolymerizable monomer, Preferably Is preferably from 15 to 40 parts by weight. When the compounding ratio of the photoinitiator of (ii) component is few, the speed | rate of photopolymerization will slow and a sensitivity will fall. On the contrary, too much sensitivity may cause the pattern line width to become thicker with respect to the pattern mask, resulting in a problem that the faithful line width cannot be reproduced with respect to the mask or the pattern edge is uneven and sharp. On the other hand, although the photoinitiator of (iii) also has a photosensitization effect, even if it adds a photosensitizer separately, it does not interfere at all.

Moreover, as a light-shielding pigment of (iv) component, black organic pigment, mixed organic pigment, light-shielding material, etc. are mentioned. Among these, as black organic pigment, perylene black, cyanine black, etc. are mentioned, for example. Examples of the mixed organic pigment include those which are similarly blackened by mixing at least two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Although two or more kinds may be appropriately selected and used, the carbon black may have light shielding properties, surface smoothness, dispersion stability, resin, It is preferable at the point that compatibility of is favorable.

The light-shielding pigment of (iv) component can be used with a dispersing agent as needed. As such a dispersing agent, surfactant, such as a cationic type, an anionic type, a nonionic type, an amphoteric, a silicone type, and a fluorine type, is mentioned, for example. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether. The usage-amount of the light-shielding pigment of (iv) component is 30-280 weight part with respect to 100 weight part of alkali-soluble resin represented by General formula (1), and (ii) component, Preferably it is the range of 50-230 weight part Is good. If it is less than these ranges, the light shielding property is not sufficient, and in order to obtain a desirable light shielding rate, the film thickness must be thickened, so that the surface smoothness of the color filter is difficult to obtain. On the contrary, when too much, the dispersion stability of the photosensitive resin composition for black matrices will fall, and since the content of the photosensitive resin used as an original binder will also decrease, it is unpreferable that the developing property is impaired and the film-form performance is impaired. There is a risk of not having a problem.

The photosensitive resin composition containing alkali-soluble resin represented by General formula (1) of (i) component, the photopolymerizable monomer of (ii) component, and the photoinitiator of (iii) component as an essential component is a color filter ink, a protective film, etc. Useful for color filter materials and the like. Furthermore, alkali-soluble resin represented by General formula (1) of (i) component, the photopolymerizable monomer of (ii) component, the photoinitiator of (iii) component, and the light-shielding pigment of (iv) component are included as an essential component. The photosensitive resin composition for black matrices is also useful as a black matrix material for color filters. These can be melt | dissolved in a solvent as needed, or can mix and use various additives.

When using the photosensitive resin composition of this invention for color filters etc., it is preferable to use a solvent other than said each component. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, and N. Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethylcarbitol and butyl Glycol ethers such as carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and ethyl acetate Butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, Acetate esters, such as butyl carbitol acetate, a propylene glycol monomethyl ether acetate, and a propylene glycol monoethyl ether acetate, etc. are mentioned, It can be set as a uniform solution composition by melt | dissolving and mixing using these.

Moreover, additives, such as a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, an antifoamer, can be mix | blended with the photosensitive resin composition of this invention as needed. Of these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol and phenothiazine. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate and tricresyl. Examples of the filler include glass fiber, silica, mica, alumina, and the like. Moreover, as an antifoamer and a leveling agent, a silicone type, a fluorine type, and an acryl type compound are mentioned, for example.

The photosensitive resin composition of this invention is alkali-soluble resin represented by General formula (1), photopolymerizable monomer of (ii), and (ii) photopolymerization in solid content (solid content contains monomer which becomes solid content after hardening) except a solvent. It is preferable that an initiator and (iv) light-shielding pigment added as needed contain 70 wt% or more in total, Preferably it is 80 wt%, More preferably, it is 90 wt% or more. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 20 to 80 wt% based on the total amount. When making the photosensitive resin composition of this invention for a color filter, it is suitable for a protective film use and a black matrix use.

The coating film (cured product) of this invention is obtained by apply | coating the solution of the said photosensitive resin composition to a board | substrate etc., for example, drying, irradiating light (including ultraviolet rays, radiation, etc.), and hardening it. By making the part which does not touch a part to which light hits, hardening only the part which hits a light, and melt | dissolving another part with alkaline solution, the coating film of a desired pattern is obtained.

Next, the manufacturing method of the color filter using the photosensitive resin composition is demonstrated. First, after apply | coating the photosensitive resin composition on the surface of a board | substrate, prebaking is performed and the solvent is evaporated and a coating film is formed. Next, after exposing through a photomask to this coating film, it develops using alkaline developing solution, dissolves and removes the unexposed part of a coating film, and post-bakes, and then forms the black matrix formed so that the part which forms a pixel may be divided. Get After apply | coating the liquid composition of the photosensitive resin composition in which the red pigment was disperse | distributed, for example on this board | substrate, prebaking is performed and the solvent is evaporated and a coating film is formed. Next, after exposing through a photomask to this coating film, it develops using alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and post-bakes, whereby the red pixel pattern was arrange | positioned in predetermined | prescribed arrangement. A pixel array is formed. Then, using the liquid composition of the photosensitive resin composition in which the green or blue pigment was disperse | distributed, it carried out similarly to the above, and apply | coats, prebakes, exposes, develops, and postbakes each liquid composition, and the green pixel array and blue By sequentially forming pixel arrays on the same substrate, the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate, and as the protective film thereon, the liquid composition of the photosensitive resin composition is made the same as above. Application | coating, prebaking, exposure, image development, and postbaking of a liquid composition are performed, and the color filter in which the protective film was formed is obtained.

When apply | coating a photosensitive resin composition to a board | substrate, in addition to a well-known solution immersion method and a spray method, any method, such as a method which uses a roller coater, a land coater, or a spinner group, can be employ | adopted. After coating to the desired thickness by these methods, a film is formed by removing (prebaking) the solvent. Prebaking is performed by heating by an oven, a hotplate, etc., vacuum drying, or combining them. The heating temperature and heating time in prebaking are suitably selected according to the solvent to be used, for example, it is performed for 1 to 10 minutes at the temperature of 80-120 degreeC.

As the radiation used when producing the color filter, for example, visible rays, ultraviolet rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used, but radiation having a wavelength in the range of 250 to 450 nm is preferable. Moreover, as a developer suitable for this alkali image development, although the aqueous solution of the carbonate of an alkali metal or alkaline-earth metal, the aqueous solution of the hydroxide of an alkali metal, etc. are mentioned, Especially, carbonates, such as sodium carbonate, potassium carbonate, lithium carbonate, are 0.05- It is preferable to develop at the temperature of 20-30 degreeC using the weakly alkaline aqueous solution containing 10 weight%, and a fine image can be formed precisely using a commercially available developer, an ultrasonic cleaner, etc. After the alkali development, it is usually washed with water. As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be applied. The developing conditions are preferably 10 to 120 seconds at room temperature.

After developing in this manner, heat treatment (post-baking) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesiveness of a patterned coating film and a board | substrate. This is done by heating with an oven, a hot plate or the like, similar to prebaking. The patterned coating film of this invention is formed through each process by the above photolithographic method.

As a board | substrate used when forming the color filter provided with a pixel and / or black matrix, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone etc.) etc. are mentioned. If necessary, these substrates may be subjected to appropriate pretreatment such as provision of a transparent electrode layer, chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, and the like.

<Examples>

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example and a comparative example. In addition, this invention does not limit the range by these Examples and a comparative example. In addition, evaluation of resin in the following Examples etc. was performed as follows unless there is a notice.

[Solid content concentration]

1 g of the resin solution (including the reaction product or alkali-soluble resin) obtained in Examples (including the comparative example) was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ (g) ], and it was determined from the weight [W ₂ (g)] after 2hr heated at 160 ℃ by the following equation.

Solid content concentration (% by weight) = 100 × (W ₂ -W ₀ ) / (W ₁ -W ₀ )

[Mountain]

The resin solution was dissolved in dioxane and titrated with 1 / 10N-KOH aqueous solution using phenolphthalein as an indicator.

[Molecular Weight]

It is the value which calculated | required weight average molecular weight (Mw) using tetrahydrofuran as a developing solvent and making it the standard polystyrene conversion value by gel permeation chromatography (GPC).

In addition, the symbol used in an Example is as follows.

FHPA: Equivalent reactant of bisphenol fluorene type epoxy resin with acrylic acid (Nippon Steel Chemical Co., ASF-400 solution: solid content concentration 50wt%, solid content equivalent acid value 1.28mgKOH / g)

FHPPA: Bis (phenylphenol) fluorene type epoxy resin and the equivalent equivalent of acrylic acid (50 wt% PGMEA solution, solid content of 7.51 mgKOH / g)

BisA-GEA: an equivalent reaction product of bisphenol A diglycidyl ether and acrylic acid (50 wt% PGMEA solution, solid value of acid value of 1.72 mgKOH / g)

BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride

BTDA: 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride

ODPA: 3,3 ', 4,4'-oxydiphenyltetracarboxylic dianhydride

CHDA: 3,3 ', 4,4'-oxydiphenyltetracarboxylic dianhydride

THPA: 1,2,3,6-tetrahydrophthalic anhydride

HHPA: Hexahydrophthalic anhydride

GMA: glycidyl methacrylate

HBAGE: 4-hydroxybutyl acrylate glycidyl ether

TEAB: tetraethylammonium bromide

TPP: triphenylphosphine

PGMEA: Propylene glycol monomethyl ether acetate

Example 1

600.00 g (0.49 mol) of 50% PGMEA solution of FHPA [component (A)], 72.75 g (0.247 mol) of BPDA [component (B)], 39.56 g of PGMEA in a 1000 ml four-necked flask with reflux cooler, and 1.30 g of TPP was added, the mixture was stirred for 2 hours under heating at 120 to 125 ° C, and further stirred for 6 hours at 70 to 75 ° C to obtain a reaction product (a). Solid content concentration of the obtained reaction product (a) was 52.4 wt%, the acid value (solid content conversion) of the resin was 78.0 mgKOH / g, and the weight average molecular weight (Mw) by GPC analysis was 3400.

Subsequently, 73.92 g (0.52 mol) of GMA [(C) component] was added to the reaction product (a), followed by stirring at 80 ° C. for 8 hours. Further, 156.71 g (1.03 mol) of THPA [(D) component] was added to the flask, followed by stirring at 80 ° C. for 7 hours to synthesize alkali-soluble resin (1) -1. Solid content of obtained alkali-soluble resin was 62.Owt%, the acid value (solid content conversion) was 111.8 mgKOH / g, Mw by GPC analysis was 3700. In addition, (A)-(D) component name and compounding ratio which were used for the synthesis | combination of alkali-soluble resin (1) -1 concerning Example 1, and the weight average molecular weight and acid value of obtained alkali-soluble resin (1) -1 are put together It shows in Table 1 (the same also about a following example and a reference example).

[Example 2]

In a 1000 ml four-necked flask with reflux condenser, 600.00 g (0.49 mol) of 50% PGMEA solution of FHPA (A), 96.02 g (0.33 mol) of BPDA [component (B)], 4.36 g of PGMEA, and 1.02 of TEAB g was added, and the mixture was stirred for 2 hours under heating at 120 to 125 DEG C, and further stirred for 8 hours at 60 to 65 DEG C to obtain a reaction product (b). Solid content concentration of obtained reaction product (b) was 57.8 wt%, acid value (solid content conversion) was 91.6 mgKOH / g, Mw by GPC analysis was 8800.

Subsequently, 93.82 g (0.66 mol) of GMA [(C) component] was added to the reaction product (b), followed by stirring at 80 ° C for 24 hours. Moreover, 153.67g (1.01mol) of THPA [(D) component] and 153.67g of PGMEA were thrown in the flask, and it stirred at 80 degreeC for 24 hours, and synthesize | combined alkali-soluble resin (1) -2. Solid content concentration of obtained alkali-soluble resin was 59.2 wt%, the acid value (solid content conversion) was 126.8 mgKOH / g, Mw by GPC analysis was 6800.

[Example 3]

In a 500 ml four-necked flask equipped with a reflux condenser, 200.0 g of the reaction product (b) obtained in Example 2 and 13.36 g (0.094 mol) of GMA [(C) component] were added thereto, and the mixture was stirred at 80 ° C. for 24 hours. 28.91 g (0.19 mo1) of THPA [(D) component] and 28.91 g of PGMEA were put into the flask, and it stirred at 80 degreeC for 24 hours, and synthesize | combined alkali-soluble resin (1) -3. Solid content concentration of obtained alkali-soluble resin was 59.2 wt%, the acid value (solid content conversion) was 100.3 mgKOH / g, Mw by GPC analysis was 6700.

Example 4

In a 500 ml four-necked flask equipped with a reflux condenser, 200.0 g of the reaction product (b) obtained in Example 2 and 27.01 g (0.19 mol) of GMA [component (C)] were added and stirred at 80 ° C. for 24 hours. 12.78 g (0.084 mol) and 12.78 g of PGMEA were thrown in THPA [(D) component], and it stirred at 80 degreeC for 24 hours, and synthesize | combined alkali-soluble resin (1) -4. Solid content concentration of obtained alkali-soluble resin was 60.5 wt%, acid value (solid content conversion) was 32.5 mgKOH / g, Mw by GPC analysis was 6400.

[Examples 5 to 14]

At least a part of the components (A) to (D) used in Example 2 were used in place of the raw materials listed in Table 1 below, that is, instead of FHPA, BPDA, THPA or GMA in Example 2, the raw materials shown in Table 1 were used. Reaction was performed similarly to Example 2 except having obtained alkali-soluble resin (1) -5-(1) -14.

[Example 15]

Reaction was performed like Example 1 except having changed the preparation amount of THPA [(D) component] in the said Example 1 into 118.68g (0.78mol), and alkali-soluble resin (1) -15 was obtained.

[Referential Example 1]

In a 500 ml four-necked flask equipped with a reflux condenser, 206.26 g (0.17 mol) of 50% PGMEA solution of FHPA, 0.085 mol of BPDA, 0.085 mol of THPA, 0.45 g of PGMEA and 0.45 g of TPP were added at 120 to 125 ° C. It stirred for 6 hours under heating, and obtained resin (reference) -1. Solid content concentration of the obtained resin solution was 55.6 wt%, the acid value (solid content conversion) was 103.0 mgKOH / g, Mw by GPC analysis was 2600.

[Reference Example 2]

In a 1000 ml four-necked flask equipped with a reflux condenser, 600.00 g (0.49 mol) of 50% PGMEA solution of FHPA, 96.02 g (0.33 mol) of BPDA, 4.36 g of PGMEA, and 1.02 g of TEAB were heated at 120 to 125 ° C. It stirred for 2 hours under stirring, and further heated and stirred for 8 hours at 60-65 degreeC, and obtained resin (reference) -2. Solid content concentration of the obtained resin solution was 58.5 wt%, acid value (solid content conversion) was 91.OmgKOH / g, and Mw by GPC analysis was 8600.

Next, the present invention will be specifically described based on Examples and Comparative Examples according to the manufacture of color filters. The present invention is not limited to these examples. Here, the raw materials and symbols used in the manufacture of the color filter according to the Examples and Comparative Examples are as follows.

(1) Components: (1) -1 to (1) -4, (Reference) -1 and (Reference) -2: Alkali-soluble resins obtained in Examples 1 to 4 and Reference Examples 1 and 2 above

(ii) -1 Component: dipentaerythritol hexaacrylate

(iii) -1 Component: Oxime ester photopolymerization initiator (Chiba Specialty Chemicals, IRGACURE 0XEOl)

(iii) -2 Component: Michler's Ketone (Sensitizer)

(v) Component: Tetramethylbiphenyl type epoxy resin

Solvent: Cellosolve Acetate

Photosensitive using alkali-soluble resin obtained by the said Examples 1-4 and Reference Examples 1-2 by mix | blending the said compounding component [(1), (ii), (iii) and (v)] in the ratio shown in Table 2. The resin composition was prepared.

(1) or (reference) (ii) -1
ingredient (ii) -1
ingredient (iii) -2
ingredient (v)
ingredient solvent ratio
(Weight ratio) 20 8.6 1.2 0.2 4.4 65.6

[Examples 16-19, Comparative Examples 1-2]

The photosensitive resin composition using the alkali-soluble resin obtained in the above Examples 1 to 4 and Reference Examples 1 to 2 was applied on the glass substrate of 125 mm x 125 mm using a spin coater so that the film thickness after postbaking was 2 m. Then, it prebaked at 90 degreeC for 2 minutes, and created the coating plate. Then, the ultraviolet-ray 10mW / cm <^2> of wavelength 365nm was irradiated for 10 second through the pattern mask with the 500W / cm <^2> high pressure mercury lamp, and the photocuring reaction of the photosensitive part was performed. Next, after the desired pattern was visualized at 25 degreeC in the 1 wt% sodium carbonate aqueous solution, this exposed coating plate was developed and washed for 20 second, and the unexposed part of the coating film was removed. Then, heat-drying process was performed for 30 minutes at 230 degreeC using the hot air dryer, and the color filter for a test was obtained. The developability, image development adhesiveness, etc. in the test color filter of Examples 16-19 and Comparative Examples 1-2 were evaluated. Specifically, the obtained samples were evaluated for the dryness of the coating film, the developability with respect to the aqueous alkali solution, the exposure sensitivity, the coating film hardness, the adhesion to the substrate, the heat resistance, and the chemical resistance. The results are shown in Table 3. In addition, various physical property data were measured on condition of the following.

(1) Drying property of coating film

The dryness of the coating film was evaluated according to JIS-K5400. The rank of evaluation is as follows.

○: no stickiness at all

(Triangle | delta): What is recognized to be extremely sticky

X: Remarkably sticky thing recognized

(2) Developability to alkaline aqueous solution

After developing a pattern at 25 degreeC in 1weight% of sodium carbonate aqueous solution, it developed by immersing for 20 second. After image development, the remaining resin was expanded to 40 times and visually evaluated. The rank of evaluation is as follows.

 (Circle): Developability is good (the thing in which resist does not remain on glass at all)

 (Triangle | delta): The developability is rather bad (resist remaining very little on glass).

 ×: poor developability (some resist left on the glass)

(3) exposure sensitivity

The exposure mask which has a 10 micrometer fine wire pattern was closely attached to the coating film, and the light quantity of 100 mJ / cm <^2> was irradiated using the 500W high pressure mercury lamp. Next, after developing a pattern at 25 degreeC in the developable 1 weight% sodium carbonate aqueous solution with respect to aqueous alkali solution, it immersed for 20 second and developed. After the development, the line width of the formed thin line pattern was evaluated (in this evaluation method, the line width becomes thicker with higher sensitivity).

(4) coating hardness

After the exposure development, the hardness of the coating film heated at 230 ° C. for 30 minutes was indicated by the test method of JIS-K5400, and the highest hardness that the coating film was not damaged when a load of 1 kg was applied using a pencil hardness tester. . The pencil used is "Mitsubishi Hi-uni".

(5) adhesion with the substrate

After exposure development, a crosscut is put into the coating film heated at 230 degreeC for 30 minutes, and it makes a peeling test using a cello tape (registered trademark), and visually examines the peeling state of the checkerboard scale. Rated by The rank of evaluation is as follows.

(Circle): Peeling is not recognized at all

×: Even if peeling is recognized even a little

(6) heat resistance

After the exposure development, the coating film heated at 230 ° C. for 30 minutes was placed in an oven at 250 ° C. for 3 hours to evaluate the state of the coating film. The rank of evaluation is as follows.

 ○: no abnormality in the appearance of the coating film

X: Gold, peeling, and coloring exist in the appearance of a coating film

(7) chemical resistance

After exposure development, the coating film heated at 230 degreeC for 30 minutes was immersed in the following chemicals on condition of the following, and the external appearance and adhesiveness after immersion were evaluated.

Acid resistance test: 24 hours in 5% HCl

Alkali resistance test 1: 24 hours immersion in 5% NaOH

Alkali resistance test 2: Soak for 10 minutes at 50 ° C in 4% KOH

Alkali resistance test 3: Soak for 5 minutes at 80 ° C in 1% NaOH

Solvent resistance test 1: Soak for 10 minutes at 40 ℃ in NMP

Solvent resistance test 2: Soak for 5 minutes at 80 ° C in NMP

NMP Co., Ltd .: N-methyl-pyrrolidone

alkali
Soluble resin Coating
Dryness Developability Exposure sensitivity
Line width Coat
Hardness Adhesiveness Heat resistance Tolerance
Character Example 16 (1) -1 ○ ○ 10.8 탆 4H ○ ○ ○ Example 17 (1) -2 ○ ○ 11.0㎛ 4H ○ ○ ○ Example 18 (1) -3 ○ ○ 10.5 탆 4H △ ○ ○ Example 19 (1) -4 ○ △ 11.0㎛ 4H ○ ○ ○ Comparative Example 1 (Reference) -1 ○ △ 9.8 μm 4H × ○ ○ Comparative Example 2 (Reference) -2 ○ × 10.1 ㎛ 4H × ○ ○

As apparent from the results of Table 3, Examples 16 to 19, particularly Examples 16 and 17, are superior in developability and adhesiveness as compared with the comparative examples. That is, the difference in solubility in the alkali developer of the hardened part and the uncured part after irradiation with ultraviolet rays or electron beams is large, and at the same time, the number of ethylenically unsaturated bond groups in one molecule can be increased to provide a cured film having good developability and high adhesion. Could know.

Next, although this invention is demonstrated concretely based on the Example and comparative example which manufacture black matrix, this invention is not limited to these. Here, the raw material and the symbol used for manufacture of the black matrix of a following Example and a comparative example are as follows.

(i) -1 component: Alkali-soluble resin obtained by the said Example 1

(i) -2 component: Alkali-soluble resin obtained in the said Example 15

(i) -3 component: Alkali-soluble resin obtained by the said Example 2

(i) -4 component: Alkali-soluble resin obtained by the said Reference Example 1

(i) -5 component: Alkali-soluble resin obtained by the said Reference Example 2

(ii) -2 Component: trimethylolpropanetriacrylate

(iii) -3 Component: Oxime ester photopolymerization initiator (Chiba Specialty Chemicals, IRGACURE 0XEO2)

(iii) -4 Component: Benzophenone Photopolymerization Initiator (Chiba Specialty Chemicals, IRGACURE 369)

(iv) -1 component: carbon dispersion (average particle size: 100-130 nm) having a pigment concentration of 20.0% and a total solid content of 24%

(iv) -2 component: carbon dispersion (average particle size: 100-150 nm) having a pigment concentration of 20.0% and a total solid content of 29%

Solvent-1: Propylene Glycol Monomethyl Ether Acetate

Solvent-2: Cyclohexanone

Additive-1: Silane Coupling Agent (SH-6040 from Dow Corning Toray)

Said compounding component was mix | blended in the ratio shown in Table 4, and the photosensitive resin composition for black resists of Examples 20-25 and Comparative Examples 3-6 were prepared. In addition, all the numerical values of Table 4 represent a weight part.

[Examples 20-25, Comparative Examples 3-6]

The photoresist composition for black resists shown in Table 4 was apply | coated so that the film thickness after postbaking might be 0.9-1.0 micrometer on the 125 mm x 125 mm glass substrate using a spin coater, and it prebaked for 1 minute at 80 degreeC, and a coating plate Was written. Then, the ultraviolet-ray of illumination intensity 100mJ / cm <^2> of wavelength 365nm was irradiated with the high pressure mercury lamp of 500W / cm <^2> , and the photocuring reaction of the photosensitive part was performed. Next, the exposed plate is developed in a 0.04wt% potassium hydroxide aqueous solution or 0.5wt% sodium carbonate aqueous solution with a shower at 24 ° C. for 30 seconds, followed by spray washing to further remove unexposed portions of the coating film. did. Then, heat-drying process was performed for 30 minutes and 230 degreeC using a hot air dryer, and the color filter concerning Examples 20-25 and Comparative Examples 3-6 was obtained.

Table 5 shows evaluation results such as developability and development margin for the color filters of Examples 20 to 25 and Comparative Examples 3 to 6 obtained above. These evaluation methods are as follows.

Film thickness:

It measured using the stylus type step measuring device (trade name P-10 by KLA-Tencor).

Developing time:

At the time of alkali development, the time required for all the patterns to be seen was recorded. When the pattern was not seen even when the developing time exceeded 120 seconds, it was set as x.

Fine wire margin:

When the part exposed by the 10 micrometer pattern mask was developed, time after which a pattern part maintained 10 +/- 1 micrometer was recorded after the pattern was shown. The line width of the pattern portion was measured using a side microscope (trade name XD-20 manufactured by Nikon Corporation).

Taper shape:

The pattern after development was observed using a scanning electron microscope (trade name: VE-780, manufactured by Keyence, Inc.). When it produced, it was set as x.

Line shape:

About the 10 micrometer line after image development, the presence or absence of linearity, a fringe, etc. of a pattern part was evaluated with the said length microscope. Therefore, it was set as << good> about good linearity and the thing which a fringe did not generate | occur | produce, and the fringe etc. generate | occur | produced and evaluated that the linearity was bad as x <defect>. Only when each item was very favorable, it evaluated as "◎."

Optical concentration:

It measured using the optical densitometer (made by Otsuka Denshi Co., Ltd.).

Example 20 Example 21 Example 22 Comparative Example 3 Comparative Example 4 Alkali-soluble resin (i) -1 (i) -2 (i) -3 (i) -4 (i) -5 Film thickness (占 퐉) 0.9 0.9 0.9 0.9 0.9 Alkali developer Potassium hydroxide solution Developing time (second) 32 47 55 89 96 Fine wire margin (sec) 20 30 30 20 30 Taper shape ○ ○ ○ × × Line shape ○ ○ ○ × × Optical density 4.78 4.84 4.75 4.86 4.72 Example 23 Example 24 Example 25 Comparative Example 5 Comparative Example 6 Alkali-soluble resin (i) -2 (i) -2 (i) -2 (i) -4 (i) -4 Film thickness (占 퐉) 1.0 1.0 1.0 - - Alkali developer Sodium carbonate solution Developing time (second) 31 31 31 31 31 Fine wire margin (sec) 40 40 40 Peeling pattern Peeling pattern Taper shape ○ ○ ○ × × Line shape ○ ○ ○ × × Optical density 4.63 4.74 4.84 4.73 4.72

As is apparent from the results of Table 5, the color filters according to Examples 20 to 25 were excellent in their respective performances, and in particular, the black matrixes of Examples 23 to 25 were superior in developability and adhesion as compared to Comparative Examples 5 and 6. Even when the usage-amount of a photoinitiator is reduced, a thin wire pattern can be formed. That is, the difference in solubility with respect to the alkaline developing solution of the hardened part and the uncured part after ultraviolet or electron beam irradiation is large, and simultaneously, the cured film which has a positive developability and high adhesiveness can be provided by increasing the number of ethylenically unsaturated bond groups in 1 molecule. And it was found.

The photosensitive resin composition of this invention has high solubility with respect to alkaline developing solution compared with the conventional thing, and since the number of ethylenically unsaturated bond groups in 1 molecule is large, the crosslinking density after hardening is high. That is, since the solubility difference with respect to the alkaline developing solution of the hardened part and the uncured part after ultraviolet-ray or electron beam irradiation becomes large, a fine pattern can be formed also in thin film or a high coloring agent concentration. Therefore, the photosensitive resin composition of this invention uses the various color display bodies, such as a color liquid crystal display device, a color facsimile, an image sensor, the coloring ink for color filters used for optical instruments, etc., and the black matrix formed by these. Eggplants can be preferably used for color filters, televisions, video monitors, computer displays and the like. It is especially preferable as a color filter protective film material and a material for black matrix formation. The color filter thus obtained is very useful, for example, in a transmissive, reflective or transflective color liquid crystal display device, a color image sensor, a color sensor, and the like.

Claims (12)

It is represented by following General formula (1), Alkali-soluble resin characterized by having a carboxylic acid residue and a polymerizable unsaturated group in a molecule | numerator. [Formula 1]

(Wherein R ₁ , R ₂ , R ₃ , And R ₄ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. And X is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -0-, 9, A 9-fluorenylene group or a direct bond is shown, and Y represents a tetravalent carboxylic acid residue. G represents a substituent having a polymerizable double bond and a carboxyl group represented by the following General Formula (2). Z represents a substituent represented by the following General Formula (3), and n represents a number from 1 to 20. (2)

(Wherein R ₈ is an aliphatic hydrocarbon group having 3 to 6 carbon atoms, R ₆ is a divalent alkylene group, R ₇ represents a hydrogen atom or a methyl group, Z is the same as the following general formula (3), and q is 0 or 1) Indicates the number of.) (3)

(Wherein L represents a divalent or trivalent carboxylic acid residue and p is 1 or 2). The reactant having a carboxyl group obtained by reacting a diol compound (A) containing a polymerizable unsaturated group with tetracarboxylic acid or its acid dianhydride (B), while containing at least one polymerizable double bond, At the same time, a reactant having a hydroxyl group is obtained by reacting an oxirane compound (C) containing one oxirane ring, followed by reacting the reactant having the hydroxyl group with dicarboxylic acid or its acid anhydride (D). Alkali-soluble resins. The molar ratio [(B) / (A)] of (A) component and (B) component when reacting said (A) component and (B) component is 50 mol% or more and less than 100 mol%. Alkali-soluble resin characterized by the above-mentioned. The molar ratio [(C) / (B)] of the component (B) and the component (C) when the component (C) is reacted with the reactant between the component (A) and the component (B) is 160. It is -220 mol%, Alkali-soluble resin characterized by the above-mentioned. The molar ratio of the component (D) according to claim 3, wherein when the reactant obtained by reacting the reactant between the component (A) and the component (B) and the component (D), the molar ratio of the component (D) is (A) It is 20-110 mol% with respect to [2x [(A)-(B)] + (C)] calculated | required from the number-of-moles of-(C) component, Alkali-soluble resin characterized by the above-mentioned. (i) an alkali-soluble resin according to any one of claims 1 to 5, (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as an essential component. Photosensitive resin composition characterized by the above-mentioned. The hardened | cured material obtained by hardening | curing the photosensitive resin composition of Claim 6. It formed by the hardened | cured material obtained by apply | coating and hardening the photosensitive resin composition of Claim 6, The color filter characterized by the above-mentioned. Oxolane containing at least one polymerizable double bond and simultaneously containing one oxirane ring in a reactant having a carboxyl group obtained by reacting a diol compound (A) containing a polymerizable unsaturated group with an acid dianhydride (B). A reaction product having a hydroxyl group is obtained by reacting a compound (C), and then an acid anhydride (D) is reacted with the reaction product having a hydroxyl group. (i) an alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in one molecule, [Chemical Formula 4]

(Wherein R ₁ , R ₂ , R ₃ , and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -0-, 9,9-fluore A nylene group or a direct bond, Y represents a tetravalent carboxylic acid residue, G represents a substituent having a polymerizable double bond and a carboxyl group, Z represents a substituent represented by the following general formula (3), and n represents 1 The number of -20 is shown.) [Chemical Formula 5]

(Wherein L represents a divalent or trivalent carboxylic acid residue and p is 1 or 2). (ii) photopolymerizable monomers having at least one ethylenically unsaturated bond (iii) a photoinitiator, and (iv) light-shielding pigments The photosensitive resin composition for black matrices containing as an essential component. Hardened | cured material obtained by hardening | curing the photosensitive resin composition for black matrices of Claim 10. It formed by the hardened | cured material obtained by apply | coating and hardening | curing the photosensitive resin composition for black matrices of Claim 10, The color filter characterized by the above-mentioned.