JP2009286904A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for a color filter protective film having good alkali developability, and affording a cured product thereof having excellent heat resistance and transparency. <P>SOLUTION: The photosensitive resin composition (Q) for the color filter protective film is used which comprises a hydrophilic resin (A), a multifunctional (meth)acrylate monomer (B), a compound (C) having at least one functional group selected from among the group consisting of an alkoxymethyl group, a methylol group, an imino group, an oxazoline group, and a glycidyl group, and a photoradical polymerization initiator (D). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a photosensitive resin composition used for forming a color filter protective film for a liquid crystal panel that can be cured and developed with light by a process including light irradiation, and a color filter protective film formed using the composition. It is.

  There are various driving methods for liquid crystal panels, such as a static driving method, a simple matrix method, and an active matrix method. In recent years, the active matrix method has become widespread as a flat display for personal computers and personal digital assistants. Yes.

A color filter in an active matrix type liquid crystal panel is usually composed of a colored layer, a planarizing material and a protective film, and the protective film, that is, the color filter protective film, protects the colored layer and flattens the color filter. Plays the role of Further, the color filter protective film is required to have excellent colorless transparency so as not to affect the color tone of the color material blended in the pixel portion.
The color filter is exposed to a high temperature during the assembly of the liquid crystal panel. For example, in the step of forming the ITO film, the color filter is heated at about 250 ° C. for about 1 hour. Therefore, the resin that forms the color filter protective film is not discolored or turbid during the high-temperature heating process, and the transparency does not deteriorate (hereinafter referred to as “heat-resistant transparency”). Is desired).

As a measure for improving heat-resistant transparency, Patent Document 1 introduces an ethylenic double bond by adding a (meth) acryloyloxyisocyanate compound to a (meth) acrylic copolymer having a carboxyl group and a hydroxyl group, It is disclosed to impart curability and improve heat-resistant transparency.
Patent Document 2 discloses a technique that can improve heat-resistant transparency using a photosensitive polyimide precursor.

Japanese Patent Laid-Open No. 11-349331 JP 2003-231752 A

However, any of the above resin compositions still has a problem that the heat-resistant transparency is not sufficient.
Accordingly, the present invention provides a photosensitive resin composition that provides a color filter protective film having good alkali developability and excellent heat-resistant transparency, and a color filter protective film obtained from the photosensitive resin composition. Is an issue.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention provides at least one functional group selected from the group consisting of a hydrophilic resin (A), a polyfunctional (meth) acrylate monomer (B), an alkoxymethyl group, a methylol group, an imino group, an oxazoline group, and a glycidyl group. And a photosensitive resin composition (Q) for a color filter protective film comprising a radical photopolymerization initiator (D) as an essential component; and the photosensitive resin composition is cured. It is a color filter protective film.

The photosensitive resin composition of the present invention and the color filter protective film obtained therefrom have the following effects.
(1) The photosensitive resin composition is excellent in alkali developability.
(2) The color filter protective film is excellent in heat-resistant transparency.

The photosensitive resin composition of the present invention comprises a hydrophilic resin (A) [hereinafter sometimes simply referred to as (A)], a polyfunctional (meth) acrylate monomer (B) [hereinafter simply referred to as (B). Or a compound (C) having at least one functional group selected from the group consisting of an alkoxymethyl group, a methylol group, an imino group, an oxazoline group and a glycidyl group [hereinafter, simply referred to as a compound (C) Or may be simply expressed as (C)], and a radical photopolymerization initiator (D) [hereinafter, it may be simply expressed as (D)]. The present invention provides a photosensitive resin composition excellent in heat-resistant transparency.
In the above and the following, for example, the expression with (meth) such as “(meth) acrylate” means “acrylate and / or methacrylate”.
In the above and the following, the “solid content” means “components other than the solvent”, and includes liquids at room temperature.

  Below, (A)-(D) which is an essential structural component of the photosensitive resin composition of this invention is demonstrated in order.

The hydrophilicity index in the hydrophilic resin (A) in the present invention is defined by HLB. Generally, the larger this value, the higher the hydrophilicity.
The preferable range of the HLB value of (A) varies depending on the resin skeleton of (A) (for example, vinyl resin, epoxy resin, polyester resin, etc.), but is preferably 4 to 19, more preferably 5 to 18, particularly preferably. 6-17. When it is 4 or more, developability is further improved when developing, and when it is 19 or less, the water resistance of the cured product is further improved. In addition, HLB in this invention is an HLB value by the Oda method, is a hydrophilicity-hydrophobicity balance value, and can be calculated from the ratio of the organic value and inorganic value of an organic compound.
HLB≈10 × inorganic / organic In addition, the inorganic value and the organic value are described on page 501 of the document “Synthesis of Surfactant and its Application” (published by Tsuji Shoten, written by Oda, Teramura); It is described in detail on page 198 of “Introduction to New Surfactants” (Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd.).

As (A), a hydrophilic vinyl resin (A1) (hereinafter sometimes simply referred to as (A1)), a hydrophilic epoxy resin (A2) (hereinafter sometimes simply referred to as (A2)), Examples include hydrophilic polyester resins, hydrophilic polyamide resins, hydrophilic polycarbonate resins, and hydrophilic polyurethane resins. (A) may be used by 1 type and may use 2 or more types together.
Among these, from the viewpoint of the photo-curing reactivity of the photosensitive resin composition (in the present invention, including both the meanings of the photo-curing speed and the photo-curing reaction rate, the same applies hereinafter) and the viewpoint of ease of production. Therefore, (A1) and (A2) are preferable.

Examples of (A1) include those having a hydrophilic group in the side chain and / or terminal of the polymer molecule. Examples of the hydrophilic group include a carboxyl group, a hydroxyl group, a sulfonic acid group, an amino group, an amide group, a polyether group, and a combination of two or more of these.
Preferred as (A1) is a hydrophilic vinyl resin having at least one hydrophilic group selected from a carboxyl group and a hydroxyl group from the viewpoint of alkali developability and heat-resistant transparency.
In order to exhibit sufficient developability, those having a hydrophilic group, particularly a carboxyl group in the side chain are particularly preferred.

  A preferred production method of (A1) is a vinyl monomer having a hydrophilic group (a) (hereinafter sometimes simply referred to as (a)) and, if necessary, a hydrophobic group-containing vinyl monomer (b) (hereinafter simply referred to as (b) ) Is sometimes vinyl-polymerized.

Examples of the vinyl monomer (a) having a hydrophilic group include the following vinyl monomers (a1) to (a7).
(A1) Hydroxyl-containing vinyl monomer:
Hydroxyalkyl (meth) acrylate [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc.], polyalkylene glycol mono (meth) acrylate [polyethylene glycol mono (meta ) Acrylate etc.], alkylol (meth) acrylamide [N-methylol (meth) acrylamide etc.], hydroxystyrene and 2-hydroxyethylpropenyl ether.
Among (a1), preferred are hydroxyalkyl (meth) acrylates, particularly 2-hydroxyethyl (meth) acrylate, from the viewpoints of alkali developability and heat-resistant transparency.

(A2) Carboxyl group-containing vinyl monomer:
Unsaturated monocarboxylic acids [such as (meth) acrylic acid, crotonic acid and cinnamic acid], unsaturated polyvalent (2-4 valent) carboxylic acids [such as (anhydrous) maleic acid, itaconic acid, fumaric acid and citraconic acid], Unsaturated polyvalent carboxylic acid alkyl (alkyl group having 1 to 10 carbon atoms) ester [maleic acid monoalkyl ester, fumaric acid monoalkyl ester, citraconic acid monoalkyl ester, etc.] and salts thereof [alkali metal salt (sodium salt) And potassium salts, etc.), alkaline earth metal salts (calcium salts and magnesium salts, etc.), amine salts and ammonium salts, etc.].
Of (a2), preferred is an unsaturated monocarboxylic acid from the viewpoint of alkali developability, and more preferred is (meth) acrylic acid.
(A3) Sulphonic acid group-containing vinyl monomer:
Examples thereof include vinyl sulfonic acid, (meth) allyl sulfonic acid, styrene sulfonic acid, α-methyl styrene sulfonic acid, 2- (meth) acryloylamido-2-methylpropane sulfonic acid, and salts thereof. Examples of the salt include alkali metal (sodium and potassium) salts, alkaline earth metal (calcium and magnesium) salts, primary to tertiary amine salts, ammonium salts and quaternary ammonium salts.

(A4) Amino group-containing vinyl monomer:
Tertiary amino group-containing (meth) acrylates [dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate)] and the like.
(A5) Amide group-containing vinyl monomer:
(Meth) acrylamide, N-alkyl (C1-6) (meth) acrylamide, diacetone acrylamide, N, N'-methylene-bis (meth) acrylamide, N, N-dialkyl (C1-6) or Diaralkyl (7 to 15 carbon atoms) (meth) acrylamide (for example, N, N-dimethylacrylamide and N, N-dibenzylacrylamide), methacrylformamide, N-methyl-N-vinylacetamide, cinnamic amide and cyclic amide (N-vinylpyrrolidone, N-allylpyrrolidone, etc.).
(A6) a quaternary ammonium base-containing vinyl monomer;
A quaternized product of a tertiary amino group-containing vinyl monomer having 6 to 50 carbon atoms (preferably 8 to 20 carbon atoms, such as methyl chloride, dimethyl sulfate, benzyl chloride and dimethyl carbonate), for example, dimethyl Examples include quaternized products of aminoethyl (meth) acrylate, quaternized products of diethylaminoethyl (meth) acrylate, quaternized products of dimethylaminoethyl (meth) acrylamide, and quaternized products of diethylaminoethyl (meth) acrylamide.
(A7) Polyether group-containing vinyl monomer:
Alkoxy (alkoxy group having 1 to 8 carbon atoms) polyalkylene (alkylene group having 2 to 4 carbon atoms) glycol mono (meth) acrylate [methoxypolyethylene glycol (degree of polymerization 2 to 40) mono (meth) acrylate and methoxypolypropylene glycol ( Polymerization degree 2-30) mono (meth) acrylate, etc.].

Of these, (a) is preferably (a1) and (a2), particularly (a2) from the viewpoint of imparting sufficient developability.

  As the hydrophobic group-containing vinyl monomer (b) used in combination with the vinyl monomer (a) having a hydrophilic group as necessary in the production of the hydrophilic vinyl resin (A1), the following nonionic monomers (b1) to (b6) Is mentioned.

(B1) (meth) acrylic acid ester;
C1-C20 alkyl (meth) acrylate of an alkyl group [for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, n-hexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, etc.]; alicyclic group-containing (meth) acrylate [dicyclopentanyl (meth) acrylate, sidiclopentenyl (meth) acrylate, isobornyl (meth) acrylate, etc. ];

(B2) an aromatic hydrocarbon monomer;
And hydrocarbon monomers having a styrene skeleton [for example, styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, and benzylstyrene] and vinylnaphthalene. It is done.
(B3) carboxylic acid vinyl ester;
Examples thereof include those having 4 to 50 carbon atoms, such as vinyl acetate, vinyl propionate and vinyl butyrate.
(B4) vinyl ether monomers;
Those having 3 to 50 (preferably 6 to 20) carbon atoms such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether and the like can be mentioned.
(B5) vinyl ketone monomer;
Examples thereof include those having 4 to 50 carbon atoms, such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(B6) a halogen atom-containing monomer;
Examples thereof include those having 2 to 50 (preferably 2 to 20) carbon atoms, such as vinyl chloride, vinyl bromide, vinylidene chloride, chlorostyrene and bromostyrene.

Among (b), (b1) is preferable from the viewpoint of photocuring reactivity, and alicyclic group-containing (meth) acrylate is more preferable.

  In (A1), the charged monomer molar ratio of (a) / (b) is usually 10 to 100/0 to 90, preferably 10 to 80/20 to 90, more preferably from the viewpoint of photocuring reactivity and developability. Is 25-85 / 15-75.

(A1) may contain a (meth) acryloyl group in the side chain for the purpose of further improving photocuring reactivity in the polymer having (a) and, if necessary, (b) as a constituent monomer. Good.
Examples of the method of incorporating a (meth) acryloyl group in the side chain include the following methods (1) and (2).
(1): A polymer is produced using a monomer having a group capable of reacting with an isocyanate group (such as a hydroxyl group or a primary or secondary amino group) in at least a part of (a), and then (meth) A method of reacting a compound having an acryloyl group and an isocyanate group (such as acryloylethyl isocyanate);
(2); producing a polymer using a monomer having a group capable of reacting with an epoxy group (hydroxyl group, carboxyl group, primary or secondary amino group, etc.) in at least a part of (a); A method of reacting a compound having a (meth) acryloyl group and an epoxy group (such as glycidyl acrylate).

The number average molecular weight of (A1) (hereinafter abbreviated as Mn. The measured value by gel permeation chromatography) is preferably 500 to 500, from the viewpoint of photocuring reactivity and developability as the photosensitive resin composition. 000, more preferably 1,000 to 100,000, and particularly preferably 3,000 to 20,000.

(A1) can be obtained by performing polymerization with a radical polymerization initiator after the monomer is diluted with a solvent (E4) if necessary. Solvents include glycol ethers (such as ethylene glycol monoalkyl ether and propylene glycol monoalkyl ether), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone), and esters (butyl acetate, ethylene glycol alkyl ether acetate and Propylene glycol alkyl ether acetate, etc.). Of the solvents (E4), ketones and esters are preferred.
When the solvent (E4) is used, the amount used is not particularly limited, but is usually 1 to 400% based on the total weight of the monomers (in the following, unless otherwise specified,% represents% by weight), preferably 5 ˜300%, particularly preferably 10˜200%.
Examples of the polymerization initiator include peroxides and azo compounds.
Peroxides include inorganic peroxides (eg, hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, etc.), and organic peroxides (eg, benzoyl peroxide, di-t-butyl peroxide, Cumene hydroperoxide, lauryl peroxide, etc.). Examples of the azo compound include azobis (2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobis (2-methylbutyronitrile), azobiscyanovaleric acid and its salts (for example, hydrochloride), and azobis (2 -Amidinopropane) hydrochloride and the like. Preferred is an azo compound. As a usage-amount of a polymerization initiator, 0.0001-20% is preferable normally based on the total weight of a monomer, More preferably, it is 0.001-15%, Most preferably, it is 0.005-10%. The reaction temperature and reaction time are appropriately determined depending on the type of radical polymerization initiator.

As described above, the hydrophilicity index of (A) is defined by HLB. Of these, the HLB value of (A1) is preferably 9 to 19, more preferably 10 to 18, particularly preferably 11 to 17. It is. If the HLB of (A1) is 9 or more, developability can be further improved.

The hydrophilic epoxy resin (A2) of (A) in the present invention has an epoxy resin skeleton containing one or more hydrophilic groups such as a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, an amide group or a polyether group. It is a polymer having.
Among (A2), preferred is a hydrophilic epoxy resin having at least one hydrophilic group selected from a carboxyl group and a hydroxyl group from the viewpoints of alkali developability and heat-resistant transparency.
(A2) preferably further has a (meth) acryloyl group in the molecule from the viewpoint of photocuring reactivity.

A preferred production method of (A2) is an epoxy resin obtained by reacting a (meth) acryloyl group-containing monocarboxylic acid with an epoxy group in an epoxy resin (A2 ₀ ) (hereinafter sometimes simply referred to as (A2 ₀ )). A method of reacting a part of the hydroxyl group with a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride (e) (hereinafter sometimes simply referred to as (e)). is there.

Examples of (A2 ₀ ) include aliphatic epoxy resins [eg, Etototo YH-300, PG-202, PG-207 (all manufactured by Tohto Kasei Co., Ltd.)] and alicyclic epoxy resins [eg, CY-179, CY-177. CY-175 (all manufactured by Asahi Kasei Epoxy Co., Ltd.)] and aromatic epoxy resins [eg, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A epoxy resin, biphenyl type epoxy resin and glycidyl modified polyvinylphenol] Can be mentioned.
Among (A2 ₀ ), an aromatic epoxy resin is preferable from the viewpoint of photocuring reactivity.
Examples of the (meth) acryloyl group-containing monocarboxylic acid used for the production of (A2) include acrylic acid and methacrylic acid.
Examples of the polyvalent carboxylic acid and polyvalent carboxylic acid anhydride (e) used in the production of (A2) include the unsaturated polyvalent carboxylic acids and anhydrides of the above-mentioned (a), and saturated polyvalent carboxylic acids. (2-6 valent) carboxylic acids (eg, aliphatic saturated polyvalent carboxylic acids such as oxalic acid, succinic acid, phthalic acid, adipic acid, dodecanedioic acid, dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid) Acids; aromatic polycarboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid and naphthalenetetracarboxylic acid) and their anhydrides (for example, Succinic anhydride, dodecenyl succinic anhydride, pentadecenyl succinic anhydride, octadecenyl succinic anhydride, etc. Aliphatic saturated polycarboxylic anhydrides; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, biphenyltetracarboxylic anhydride and naphthalenetetracarboxylic Aromatic polyhydric carboxylic acid anhydrides such as acid anhydrides). A saturated polycarboxylic acid anhydride is preferred from the viewpoint of photocuring reactivity and developability.

In the production of (A2), the charged weight ratio of (meth) acrylic acid / (A2 ₀ ) is preferably such that the concentration of (meth) acryloyl group in (A2) (measurement method will be described later) is 1.0 mmol / g or more. (Meth) acrylic acid charge weight ratio as follows. From the above viewpoint, the weight ratio of acrylic acid / (A2 ₀ ) is preferably 0.072 or more / 1, and more preferably 0.079 to 0.72 / 1. The weight ratio of methacrylic acid is preferably 0.092 or more / 1, more preferably 0.10 to 0.92 / 1, from the above viewpoint.
The reaction temperature in the reaction between (A2 ₀ ) and (meth) acrylic acid is not particularly limited, but is preferably 70 to 110 ° C. The reaction time is not particularly limited, but is preferably 5 to 30 hours. Further, if necessary, a catalyst (for example, triphenylphosphine) and a radical polymerization inhibitor (hydroquinone, p-methoxyphenol, etc.) may be used.
The charged equivalent of the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (e) with respect to the weight of the (meth) acrylic acid adduct of (A2 ₀ ) is the acid value of (A2) (the method for measuring the acid value is Is a charge equivalent of (e) such that it is preferably 10 to 500 mg KOH / g. For example, when (e) is a divalent carboxylic acid or an anhydride thereof, the charge equivalent of (e) / ( The weight of the (meth) acrylic acid adduct of A20) is preferably 0.18 to 8.9 meq / g, more preferably 0.53 to 7.1 meq / g, from the above viewpoint.
The reaction temperature in the reaction of the (A2 ₀ ) (meth) acrylic acid adduct and (e) is not particularly limited, but is preferably 70 to 110 ° C. The reaction time is not particularly limited, but is preferably 3 to 10 hours.

  Mn of (A2) is usually 500 to 3,000, preferably 1,000 to 2,800, particularly preferably 1,500 to 2, from the viewpoint of photocuring reactivity and developability as the photosensitive resin composition. , 500.

  The HLB value of (A2) is preferably 4 to 14, more preferably 5 to 13, and particularly preferably 6 to 12. If the HLB of (A2) is 4 or more, the developability can be satisfactorily exhibited.

  The solubility parameter (hereinafter referred to as SP value) of the hydrophilic resin (A) in the present invention is preferably 7 to 14, more preferably 8 to 13, and particularly preferably 11 to 13. When it is 7 or more, the developability can be further improved, and when it is 14 or less, the water resistance of the cured product is further improved.

The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147-154)"
Those with close SP values are easy to mix with each other (highly dispersible), and those with a distant numerical value are indexes indicating that they are difficult to mix.

As described above, (A) preferably has a carboxyl group from the viewpoint of developability, and the content of the carboxyl group is indicated by an acid value.
When the acid value of (A) is 10 mgKOH / g or more, developability is more likely to be exhibited, and when it is 500 mgKOH / g or less, the water resistance of the cured product can be further improved.

The acid value in the present invention can be measured by an indicator titration method using an alkaline titration solution.
The method is as follows.
(I) About 1 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then a neutral methanol / acetone solution (a mixture of acetone and methanol at 1: 1 (volume ratio)) is added and dissolved.
(Ii) Add several drops of phenolphthalein indicator and titrate with 0.1 mol / L potassium hydroxide titration solution. The end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.
(Iii) Determine using the following equation.
Acid value (KOHmg / g) = (A × f × 5.61) / S
However, A: The number of mL of 0.1 mol / L potassium hydroxide titration solution.
f: Potency of 0.1 mol / L potassium hydroxide titration solution
S: Sampling amount (g)

In the photosensitive resin composition (Q) of the present invention, (A) is preferably 10 to 70%, more preferably 15 to 65%, particularly preferably 20 to 60% based on the solid content weight of (Q). contains.
When it is 10% or more, the developability can be further improved, and when it is 50% or less, the photocuring reactivity of the cured product is further improved.

  In the present invention, the polyfunctional (meth) acrylate monomer (B) used as one essential component in the photosensitive resin composition is not particularly limited as long as it is a known polyfunctional (meth) acrylate monomer. Bifunctional (meth) acrylate (B1), trifunctional (meth) acrylate (B2), and 4-6 functional (meth) acrylate (B3).

  Examples of the bifunctional (meth) acrylate (B1) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and polyethylene glycol di (meth). Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate ( SP value of methacrylate = 12.5, SP value of acrylate = 10.3), 1,9-nonanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, 3-methyl-1, -Pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, di (ethylene oxide adduct of bisphenol A ( Examples include (meth) acrylate, di (meth) acrylate of propylene oxide adduct of bisphenol A, and neopentyl glycol di (meth) acrylate of hydroxypivalate.

  As trifunctional (meth) acrylate (B2), glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate (SP value of methacrylate = 12.5, SP value of acrylate = 10.3), pentaerythritol tri Examples include (meth) acrylate (SP value of methacrylate = 12.5, SP value of acrylate = 10.3), tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane, and the like.

  As the 4- to 6-functional (meth) acrylate (B3), pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate (methacrylate SP value = 12.5, acrylate SP value = 10.3), Examples include dipentaerythritol hexa (meth) acrylate (SP value of methacrylate = 12.5, SP value of acrylate = 10.3).

  The SP value of (B) is preferably 8 to 13, more preferably 9 to 13, particularly 9 to 12, especially 9.5 to 11, from the viewpoint of compatibility with (A).

  Preferred among (B) are (B2) and (B3), more preferably pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, and combinations thereof. Examples of (B) that can be easily obtained from the market include Light Acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-403 (manufactured by Toagosei Co., Ltd.), Light Acrylate PE-3A (Kyoeisha Chemical ( Co., Ltd.), Neomer DA-600 (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

Moreover, (B) in this invention may contain the photosensitive acrylic oligomer (B4) in the one part.
Examples of (B4) include urethane acrylate, polyester acrylate, and polyether acrylate having Mn of 1,000 or less and containing no carboxyl group and having two or more acryloyl groups in one molecule.
The content of (B4) in (B) is preferably 50% or less, more preferably 30% or less.

The content of (B) based on the weight of the solid content of (Q) is preferably 20 to 85%, more preferably 25 to 75%, and particularly preferably 30 to 70%. If it is 20% or more, the heat-resistant transparency of the cured product is further preferable, and if it is 85% or less, the developability is further improved.

  As the compound (C) having a functional group selected from the group consisting of an alkoxymethyl group, a methylol group, an imino group, an oxazoline group, and a glycidyl group, which is included as an essential component in the photosensitive resin composition (Q) in the present invention, The following compounds can be mentioned.

(I) Alkoxymethyl group-containing compound Methoxymethyl group-containing melamine compound (commercially available product such as “Cymel 300” manufactured by Mitsui Cyanamid Co., Ltd.), butoxymethyl group-containing melamine compound (commercially available product such as “Cymel 1156”: Mitsui Cyanamid) Product), butoxymethyl group-containing benzoguanamine compounds (commercially available products such as “Cymel 1123”: Mitsui Cyanamid Co., Ltd.), butoxymethyl group-containing glycoluril compounds (commercially available products such as “Cymel 1170”: Mitsui Cyanamid ( Etc.)
(I) Methylol group-containing compound Methylol group-containing melamine compound (commercially available product such as “Cymel 370” manufactured by Mitsui Cyanamid Co., Ltd.), methylol group-containing glycoluril compound (commercially available product such as “Cymel 1172”: Mitsui Cyanamid Co., Ltd.) )), Methylol group-containing urea compounds (for example, “UFR300” manufactured by Mitsui Cyanamid Co., Ltd.)
(Ii) Imino group-containing compound Imino group-containing melamine compound (commercially available product such as “Cymel 325” manufactured by Mitsui Cyanamid Co., Ltd.), imino group-containing benzoguanamine compound (commercially available product such as “Cymel 1128”: Mitsui Cyanamid Co., Ltd.) Etc.)
(Iii) Oxazoline group-containing compound Methyl oxazoline, ethyl oxazoline, oxazoline group-containing (meth) acrylic resin (commercially available products such as “Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd.), oxazoline group-containing styrene resin, etc.
(Iv) Glycidyl group-containing compound Bisphenol A type epoxy resin (for example, “Epicoat 828” manufactured by Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin (for example, “Epicoat 807” as a commercially available product: Japan Epoxy Resin ( Co., Ltd.), cresol novolac type epoxy resin (commercially available product such as “EOCN-102S”: manufactured by Nippon Kayaku Co., Ltd.), cyclic aliphatic polyglycidyl ether (commercially available product such as “CY-175”: Ciba (Manufactured by Geigy Co., Ltd.), aliphatic polyglycidyl ether, etc. (for example, “Epolite 100MF” as a commercial product: manufactured by Kyoeisha Chemical Co., Ltd.)
Among these, 1 type (s) or 2 or more types can be used.

  Of these compounds having functional groups, preferred are alkoxymethyl group-containing compounds, methylol group-containing compounds, and imino group-containing compounds, more preferred are alkoxymethyl group-containing compounds, and particularly preferred are methoxymethyl groups. A melamine compound containing and a butyroxymethyl group-containing glycoluril compound.

The photosensitive resin composition (Q) of the present invention contains a relatively high concentration of (meth) acryloyl group in (Q) and contains (C), so that curing by heat proceeds and curing It has high hardness and excellent heat resistance and transparency.
The content of (C) based on the weight of the solid content of (Q) is preferably 1 to 40%, more preferably 3 to 30%, and particularly preferably 5 to 25%. If it is 1% or more, particularly 3% or more, the curing rate, the hardness of the cured product and the heat-resistant transparency can be exhibited more satisfactorily, and if it is 40% or less, the developability can be further exhibited.

  Examples of the photo radical polymerization initiator (D) used as one essential component in the photosensitive resin composition (Q) include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, benzophenone, methylbenzoyl formate, isopropylthioxanthone, 4,4-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, anthraquinone, 2-methylanthraquinone, 2-ethyl Anthraquinone, tert-butylanthraquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-dieto Siacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-1- Propanone, 2-chlorothioxanthone, diethylthioxanthone, isopropylthioxanthone, diisopropylthioxanthone, Michler's ketone, benzyl-2,4,6- (trihalomethyl) triazine, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, 1,3-bis (9-acridinyl) propane, dimethylbenzyl ketal, trimethylbenzoyldiphenylphosphi Oxide, tribromomethylphenylsulfone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butan-1-one, and the like. (D) may be used alone or in combination of two or more.

  (D) can be easily obtained as a commercially available product. For example, as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone, Irgacure 907, 2-benzyl- Examples of 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one include Irgacure 369 (manufactured by Ciba Specialty Chemicals).

  The content of (D) based on the weight of the solid content of the photosensitive resin composition (Q) is preferably 0.01 to 15%, more preferably 0.1 to 10%, and particularly preferably 0.5 to 7%. .5%. If it is 0.01% or more, the photocuring reactivity can be exhibited more satisfactorily, and if it is 15% or less, the resolution can be further improved.

The photosensitive resin composition (Q) may contain other components (E) as long as it does not impair the effects of the present invention.
(E) includes inorganic fine particles (E1), sensitizer (E2), polymerization inhibitor (E3), solvent (E4), and other additives (for example, silane coupling agents, dyes, fluorescent brighteners). , Yellowing inhibitors, antioxidants, antifoaming agents, deodorants, fragrances, bactericides, antibacterial agents, fungicides, etc.).

As the inorganic fine particles (E1), metal oxides and metal salts can be used.
Examples of the metal oxide include titanium oxide, silicon oxide, and aluminum oxide.
Examples of the metal salt include calcium carbonate and barium sulfate.
Of these, metal oxides are preferable from the viewpoint of heat-resistant transparency and chemical resistance, and silicon oxide and titanium oxide, and particularly silicon oxide are more preferable.
The inorganic fine particles have a volume average primary particle diameter of 1 to 200 nm, preferably from 1 to 150 nm, more preferably from 1 to 120 nm, and particularly preferably from 5 to 20 nm, from the viewpoint of transparency.

  The content of (E1) based on the weight of the solid content of the photosensitive resin composition (Q) is usually 0 to 50%, preferably 1 to 45%, particularly preferably 2 to 40%. If it is 50% or less, the developability can be further improved, and if it is 2 to 40%, the heat-resistant transparency is particularly excellent.

  As the sensitizer (E2), nitro compounds (for example, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p, p'-tetramethyldiaminobenzophenone, carbonyl compounds such as chloranil, nitrobenzene, p -Dinitrobenzene and 2-nitrofluorene), aromatic hydrocarbons (eg anthracene and chrysene), sulfur compounds (eg diphenyl disulfide etc.) and nitrogen compounds (eg nitroaniline, 2-chloro-4-nitroaniline) , 5-nitro-2-aminotoluene, tetracyanoethylene and the like.

  The content of the sensitizer (E2) based on the weight of the photopolymerization initiator (D) is usually 0.1 to 100%, preferably 0.5 to 80%, particularly preferably 1 to 70%.

  There is no limitation in particular as a polymerization inhibitor (E3), What is used for normal reaction is used. Specifically, diphenylhydrazyl, tri-p-nitrophenylmethyl, N- (3-N-oxyanilino-1,3-dimethylbutylidene) aniline oxide, p-benzoquinone, p-tert-butylcatechol, nitrobenzene, Examples include picric acid, dithiobenzoyl disulfide, and copper (II) chloride.

  The content of the polymerization inhibitor (E3) based on the weight of the solid content of the photosensitive resin composition (Q) is preferably 0 to 1.0%, more preferably 0.01 to 0.5%, particularly preferably. 0.02 to 0.1%.

  As a solvent (E4), the thing similar to the solvent used for manufacture of above-mentioned (A) can be used. When the solvent is used, the amount of the solvent is not particularly limited, but is preferably 30 to 90%, more preferably 30 to 80%, of the weight of the photosensitive resin composition (Q) including the solvent. . In addition, the solvent used for manufacture of above-mentioned (A) and (B) is also contained in the compounding quantity of a solvent.

The total content of components other than the solvent (E4) in (E) is usually 80% or less, preferably 70% or less, of the solid content of the photosensitive resin composition (Q).

  The photosensitive resin composition (Q) of the present invention is prepared by mixing and / or mixing the above-described components with a known stirring and mixing device such as a planetary mixer, three rolls, a bead mill, a disper mill, a high-pressure homogenizer, and a kneader. It can be obtained by dissolving.

  The photosensitive resin composition (Q) of the present invention is usually liquid at room temperature, and its viscosity is 0.1 to 100 mPa · s, preferably 1 to 30 mPa · s at 25 ° C. The viscosity can be measured with a BL type viscometer.

As described above, the cured product of the photosensitive resin composition of the present invention is excellent in heat-resistant transparency. The photosensitive resin composition of the present invention has a light transmittance of 400 nm and 540 nm after heat treatment at 250 ° C. for 1 hour on a cured coating film having a thickness of 2.8 μm. The photosensitive resin composition is preferably 95% or more, and more preferably 96.5% or more, even in the case of the light having the above wavelength.
The above transmittance can be measured by the following method.
(1) A photosensitive resin composition is applied to the surface of a glass substrate (thickness 1 mm) so that the thickness of the cured coating film is 2.8 μm, and an ultraviolet exposure device (HMW-661F manufactured by Oak Manufacturing Co., Ltd.). Is irradiated with an exposure amount of 100 mJ and cured.
(2) About the obtained cured coating film, the transmittance | permeability (UV2400PC made by Shimadzu Corp.) was measured for the transmittance | permeability (%) of 400 nm and 540 nm after heating in a circulating air dryer of 250 +/- 2 degreeC for 1 hour. Use and measure.
The photosensitive resin composition (Q) of the present invention is particularly suitable as a photosensitive resin composition for a color filter protective film because the cured product is excellent in heat-resistant transparency.

Hereinafter, the color filter protective film of the present invention will be described.
The color filter protective film of the present invention is a color filter protective film formed by curing the photosensitive resin composition (Q).

The color filter protective film of the present invention is a protective film formed on a colored resist cured product (colored layer) on a glass substrate for a liquid crystal panel, and the process of forming the protective film is usually performed as follows.
(1) The photosensitive resin composition is applied to the entire surface of the cured colored resist on the glass substrate in a thickness of usually 0.5 to 100 μm, preferably 1 to 10 μm.
Examples of the coating method include a coating method such as a spin coater, a slit coater, a screen printing machine, a roll coater or a curtain coater, a coating method using a spray, a brush or a spatula, and a coating method by dipping. .

(2) A negative film is adhered on the photosensitive resin composition applied.
(3) Irradiate light from the upper part of the negative film, and if necessary, further heat cure to form a cured coating film.
The curing method usually includes a method using only light irradiation and a method using a combination of heat curing, but it is preferable to use a combination of two methods of curing after curing by light irradiation.
The following irradiation light sources are suitable for curing with light. For example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, metal halogen lamp, electron beam irradiation device, X-ray irradiation device, laser (argon laser, dye laser, nitrogen laser, helium cadmium laser, etc.) There is. Of these, high pressure mercury lamps and ultrahigh pressure mercury lamps are preferred.
As the heating device, a normal air circulation dryer, an electric furnace, a gas furnace, a far infrared furnace, or the like can be used.

  The heating temperature is usually 60 ° C. or higher, preferably 80 ° C. to 150 ° C. The curing time is 1 minute to 45 minutes, preferably 5 minutes to 20 minutes.

(4) Develop.
Examples of the developer include ordinary industrial water, clean water, ion-exchanged water, an aqueous solution of a normal surfactant, an inorganic acid, an aqueous solution of an organic acid, an alcoholic organic solvent, and an aqueous solution thereof. Also good.

As the surfactant, usual cationic surfactants, anionic surfactants, and nonionic surfactants can be used.
The surfactant is usually used at a concentration of 0.01 to 2%, preferably 0.05 to 1%.
Examples of inorganic acids include boric acid, phosphoric acid, hydrochloric acid, and sulfuric acid, and examples of organic acids include acetic acid, formic acid, tartaric acid, and hydroxyacetic acid.
Inorganic acids and organic acids are usually used at a concentration of 0.1 to 10%, preferably 0.5 to 5%.

  Examples of the developing method include methods such as showering, spraying and dipping. Of these, a shower is preferable.

(5) Thermosetting after development As the heating device, the same conventional air circulation dryer, electric furnace, gas furnace, far-infrared furnace, and the like as described above can be used.

  The heat curing temperature is usually 150 ° C. or higher, preferably 180 ° C. to 250 ° C. The curing time is 10 minutes to 120 minutes, preferably 30 minutes to 90 minutes.

  EXAMPLES Hereinafter, although an Example and a manufacture example demonstrate this invention concretely, this invention is not limited to these. Hereinafter, the part means part by weight.

[Production of hydrophilic resin (A)]
<Production Example A-1>
A glass Kolben equipped with a heating / cooling / stirring measure, a reflux condenser, a dropping funnel and a nitrogen inlet tube, isobornyl methacrylate 50 parts (33 mol%), 2-hydroxyethyl methacrylate 30 parts (33 mol%), methacryl 20 parts (34 mol%) of acid and 150 parts of cyclohexanone were charged and heated to 80 ° C.
A solution in which 5 parts of azobisisobutyronitrile (V-60: Wako Pure Chemical Industries, Ltd., hereinafter referred to as AIBN) prepared in advance is dissolved in 50 parts of cyclohexanone after replacing the gas phase part in the system with nitrogen. 55 parts are dropped into Kolben at 80 ° C. over 10 minutes, and further reacted at the same temperature for 3 hours to obtain a hydrophilic resin (A-1) having a hydroxyl group and a carboxyl group (Mn: 8,800, SP value: 11. 86, an HLB value: 11.98, an acid value: 102 mgKOH / g) was obtained (the solid content was 25%).
In addition, Mn is GPC measurement equipment (HLC-8120GPC, manufactured by Tosoh Corp.), column (TSKgel GMHXL 2 + TSKgel Multipore HXL-M, manufactured by Toso Corp.), polystyrene conversion measured by GPC method. Obtained as a value. The SP value, HLB value, and acid value were determined as described above. The same measurement method is used for the following production examples and comparative examples.

<Production Example A-2>
In the same Kolben as in Production Example A-1, 200 parts of a cresol novolac type epoxy resin “EOCN-1020” (manufactured by Nippon Kayaku, epoxy equivalent 200) and 245 parts of propylene glycol monomethyl ether acetate are charged and heated to 110 ° C. It was dissolved uniformly. Subsequently, 76 parts (1.07 mol part) of acrylic acid, 2 parts of triphenylphosphine, and 0.2 part of p-methoxyphenol were charged and reacted at 110 ° C. for 10 hours. The reaction product was further charged with 91 parts (0.60 mol part) of tetrahydrophthalic anhydride, further reacted at 90 ° C. for 5 hours, and after cooling, propylene glycol monomethyl ether acetate was added to adjust the solid content, and carboxyl group and acryloyl A propylene glycol monomethyl ether acetate solution of a hydrophilic resin (A-2) having a group (Mn: 2,200, SP value: 11.26, HLB value: 6.42, acid value: 91 mgKOH / g) was obtained ( Solids content is 25%).

<Comparative Production Example 1>
In the same Kolben as in Production Example A-1, 200 parts of cresol novolac resin (EP-4020G manufactured by Asahi Organic Materials Co., Ltd.) and 238 parts of propylene glycol monomethyl ether acetate were charged and heated to 110 ° C. to be uniformly dissolved. . Subsequently, 0.1 part of dibutyltin dilaurate and 20 parts of isocyanatoethyl methacrylate were added, reacted at 60 ° C. for 5 hours, and then diluted with propylene glycol monomethyl ether acetate to a solid content of 25%. , A propylene glycol monomethyl ether acetate solution of a resin (A-1 ′: Mn: 2,100, SP value: 13.46, HLB value: 6.41, acid value: 0 mg KOH / g) was obtained (solid content was 25%).

<Examples 1-5 and Comparative Examples 1-4>
[Production of photosensitive resin composition]
Number of blending parts in Table 1 [apparent parts by weight of each component. In (), according to the weight% of the solid content of each component based on the weight of the solid content of the photosensitive resin composition (Q) (rounded to one decimal place)], each raw material is charged into a glass container, Stir until uniform, and further add an additional solvent (propylene glycol monomethyl ether acetate), photosensitive resin compositions (Q1) to (Q5) of the examples, and photosensitive resin compositions (Y1) of the comparative examples (Y4) was produced.

In addition, the compound described by the abbreviation in the table | surface represents the following.
B-1 (polyfunctional (meth) acrylate): “Neomer DA-600” (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate: manufactured by Sanyo Chemical Industries, Ltd.)
B-2: (Polyfunctional (meth) acrylate): “Light acrylate PE-4A” (pentaerythritol tetra (meth) acrylate: manufactured by Kyoeisha Chemical Co., Ltd.),
C-1 (compound having a reactive functional group): “Cymel 300” (alkoxymethyl group-containing melamine compound: manufactured by Mitsui Cyanamid Co., Ltd.),
C-2 (compound having a reactive functional group): “Cymel 370” (methylol group-containing melamine compound: manufactured by Mitsui Cyanamid Co., Ltd.),
D-1 (photo radical polymerization initiator): “Irgacure 819” (bistrimethylbenzoylphenylphosphine oxide: manufactured by Ciba Specialty Chemicals),
D-2 (photo radical polymerization initiator): “Darocur TPO” (trimethylbenzoyldiphenylphosphine oxide: manufactured by Ciba Specialty Chemicals),

<Evaluation method and evaluation results>
(1) Developability The photosensitive resin compositions (Q1) to (Q5) of the present invention and the comparative photosensitive resin compositions (Y1) to (Y4) are each finished on a glass substrate with a final film thickness of 5 μm. Then, the film was spin-coated so as to be dried at 25 ° C. for 5 minutes, and then developed with a 1% sodium carbonate aqueous solution for 30 seconds to evaluate the developability.
The results are shown in Table 2. The evaluation criteria are as follows.
A: There is no residue visually.
○: There is a slight residue visually.
Δ: There are many residues by visual inspection.

(2) Heat-resistant transparency The photosensitive resin composition was applied onto the entire surface of the patterned glass substrate and dried at 80 ° C. for 20 minutes. Next, a negative film was adhered to the substrate, and after exposure, a pattern was formed by developing with a 1% aqueous sodium carbonate solution. Next, this substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate having a cured coating film.
The evaluation board | substrate which has a cured coating film was heat-processed at 250 degreeC * 1 hour, and the transmittance | permeability of the wavelength light of 400 nm and 540 nm was measured. The results are shown in Table 2 as heat resistant permeability (%).
(Transmissivity meter: UV2400PC manufactured by Shimadzu Corporation)

  As can be seen from Table 2, by using the photosensitive resin composition of the present invention, a color filter protective film having good developability and excellent heat-resistant transparency can be formed.

The photosensitive resin composition of this invention can be used conveniently for a color filter protective film.
In addition to various resist materials, such as protective films for TFT substrates, photo solder resists for printed wiring boards, photosensitive resist films, photosensitive resin relief plates, screen plates, photoadhesives or hard coat agents, etc. It is suitable as a photosensitive resin composition.
Furthermore, photosensitive coating agents for various materials such as metals (eg, iron, aluminum, titanium, copper, etc.), plastics (eg, polycarbonate, polyethylene terephthalate, poly (meth) acrylate), paper, glass, rubber and wood. It can also be used as a paint, printing ink and adhesive, and can also be applied as a molding material.

Claims (4)

  Compound (C) having at least one functional group selected from the group consisting of hydrophilic resin (A), polyfunctional (meth) acrylate monomer (B), alkoxymethyl group, methylol group, imino group, oxazoline group and glycidyl group ) And a photopolymerizable resin composition (Q) for a color filter protective film comprising a radical photopolymerization initiator (D) as an essential component.   The photosensitive resin composition (Q) according to claim 1, wherein the hydrophilic resin (A) is a hydrophilic resin having a (meth) acryloyl group and a carboxyl group.   Based on the weight of the solid content of the photosensitive resin composition, the hydrophilic resin (A) is 10 to 50% by weight, the polyfunctional (meth) acrylate monomer (B) is 20 to 85% by weight, and the compound (C) is 1 The photosensitive resin composition (Q) according to claim 1 or 2, comprising -40 wt% and 0.01-10 wt% of a radical photopolymerization initiator (D).   A color filter protective film formed by curing the photosensitive resin composition according to claim 1.