JP4680867B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition for a color filter substrate protective film, which is cured by a process including light irradiation and can be developed with an alkali, and a color filter substrate protective film formed using the composition.

  In a liquid crystal panel, a display side substrate and a liquid crystal driving side substrate are opposed to each other, a liquid crystal compound is sealed between them to form a thin liquid crystal layer, and the liquid crystal alignment in the liquid crystal layer is electrically controlled by the liquid crystal driving side substrate. Then, display is performed by selectively changing the amount of transmitted light or reflected light of the display side substrate.

  There are various types of liquid crystal panels such as static drive, simple matrix, and active matrix, but in recent years, color liquid crystal using an active matrix liquid crystal panel as a flat display for personal computers and personal digital assistants. Display devices are becoming popular.

The color filter protective film in the active matrix liquid crystal panel is required to have excellent transparency so as not to affect the color tone of the color material blended in the pixel portion. In particular, the color filter is exposed to a high temperature during the assembly of the liquid crystal panel. For example, in the process of forming the ITO film, the color filter is heated at about 250 ° C. for about 1 hour. Therefore, it is desirable that the resin forming the color filter protective film is excellent in heat-resistant transparency so as not to cause discoloration during such a high-temperature heating process and cause problems such as a decrease in transparency.
In addition, it is particularly important to make the cell gap uniform in order to suppress display unevenness, and high flatness is required for the color filter protective film.

On the other hand, in Patent Document 1, a (meth) acryloyloxyisocyanate compound is added to a (meth) acrylic copolymer having a carboxyl group and a hydroxyl group to introduce an ethylenic double bond, thereby imparting photocurability. And improving heat-resistant transparency.
Patent Document 2 discloses a technique capable of improving flatness by using a low molecular weight polymer.

Japanese Patent Laid-Open No. 11-349331 Japanese Patent Laid-Open No. 9-100360

However, even with the above resin composition, there is a problem that heat-resistant transparency and flatness are not sufficient.
The present invention provides a photosensitive resin composition that provides a color substrate protective film having good alkali developability, heat resistance transparency, and flatness, and a color filter substrate protective film obtained from the photosensitive resin composition The task is to do.

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 contains a hydrophilic polymer (A), a polyfunctional (meth) acrylate monomer (B), a polysiloxane (C) having two or more hydrolyzable alkoxy groups, and a radical photopolymerization initiator (D). The polysiloxane (C) is a condensate containing a silane compound (c1) represented by the following general formula (1) as an essential constituent monomer, and is a photosensitive resin composition for a color filter substrate protective film (Q ); And a protective film provided to protect the color filter, which is formed by curing the photosensitive resin composition by a process including light irradiation.

In the formula, R ¹ is one or more selected from the group consisting of a (meth) acryloyloxyalkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group having 1 to 6 carbon atoms in the alkyl group. R ² is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 0 or 1. is there.

The photosensitive resin composition of the present invention and the color filter substrate protective film obtained therefrom have the following effects.
-The photosensitive resin composition is excellent in alkali developability.
・ Excellent heat-resistant transparency.
・ Excellent flatness.

The thermosetting resin composition of the present invention comprises a hydrophilic polymer (A) [hereinafter sometimes referred to simply as (A)], a polyfunctional (meth) acrylate monomer (B) [hereinafter referred to simply as (B )], A polysiloxane (C) having two or more hydrolyzable alkoxy groups [hereinafter sometimes simply referred to as polysiloxane (C), or simply (C)], and It contains a photo-radical polymerization initiator (D) [hereinafter, it may be simply expressed as (D)], and (C) is a specific polysiloxane, so that it has excellent heat-resistant transparency and flatness. A curable resin composition is provided.
In the above and the following, for example, the expression with (meth) such as “(meth) acrylate” means “acrylate and / or methacrylate”.

  Hereinafter, (A) to (D), which are essential components of the thermosetting resin composition of the present invention, will be described 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, the developing property is further improved when developing the photo spacer, 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 in the document “Surfactant Synthesis and Applications” (published by Tsuji Shoten, Oda, Teramura), page 501; 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, (A1) and (A2) are preferable from the viewpoint of photocuring reactivity of the photosensitive resin composition and the viewpoint of ease of production.

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.

  Examples of the hydrophobic group-containing vinyl monomer (b) include the following nonionic monomers (b1) to (b6).

(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) is a polymer having (a) and, if necessary, (b) as a constituent monomer.
For the purpose of exerting photocuring reactivity, a (meth) acryloyl group may be further contained in the side chain.
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. Measured value by gel permeation chromatography) is developability as a photosensitive resin composition and photo-curing reactivity when containing a (meth) acryloyl group. In view of the above, it is preferably 500 to 500,000, 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 as 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 above solvents, ketones and esters are preferred.
When a solvent is used, the amount used is not particularly limited, but is usually 1 to 400% based on the total weight of monomers (in the following, unless otherwise specified,% represents% by weight), preferably 5 to 300%. Especially preferably, it is 10 to 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) in the present invention (A) (hereinafter sometimes simply referred to as (A2)) is 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 an epoxy resin skeleton containing one or more hydrophilic groups such as.
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 method for producing (A2) having a (meth) acryloyl group in the molecule is the (meth) acryloyl group on the epoxy group in the epoxy resin (A2 ₀ ) (hereinafter sometimes simply referred to as (A2 ₀ )). A group-containing monocarboxylic acid is reacted to open a ring of an epoxy group to form a hydroxyl group, and a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride (e) (hereinafter simply referred to as (e)) is part of the hydroxyl group. Is a method of reacting.

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 curability.
Acrylic acid and methacrylic acid are mentioned as a (meth) acryloyl group containing monocarboxylic acid used for manufacture of (A2) which has a (meth) acryloyl group in a molecule | numerator.
As the polyvalent carboxylic acid and polyvalent carboxylic acid anhydride (e) used in the production of (A2) having a (meth) acryloyl group in the molecule, the unsaturated polyvalent carboxylic acid of (a) described above And their anhydrides, and saturated polyvalent (2-6 valent) carboxylic acids such as oxalic acid, succinic acid, phthalic acid, adipic acid, dodecanedioic acid, dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl Aliphatic saturated polycarboxylic acids such as succinic acid; aromatic polyhydric carboxylic acids such as tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid and naphthalenetetracarboxylic acid Acid) and their anhydrides (eg, succinic anhydride, dodecenyl succinic anhydride, pentadecenyl succinic anhydride) And aliphatic saturated polycarboxylic anhydrides such as octadecenyl succinic anhydride; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, biphenyltetracarboxylic Aromatic anhydrides such as acid anhydrides and naphthalenetetracarboxylic acid anhydrides). A saturated polycarboxylic acid anhydride is preferable from the viewpoint of reactivity and developability.

The preparation weight ratio of (meth) acrylic acid / (A2 ₀ ) in the production of (A2) having a (meth) acryloyl group in the molecule is preferably (A2) having a (meth) acryloyl group in the molecule. The weight ratio of (meth) acrylic acid is such that the concentration of the (meth) acryloyl group is 1.0 mmol / g or more. 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 ) has a (meth) acryloyl group in the molecule (A2) The acid value of (e) is a charge equivalent of (e) such that the acid value is preferably 10 to 500 mgKOH / g. For example, (e) is a divalent carboxylic acid or an anhydride thereof. In this case, the weight of the (e) charged equivalent / (A2 ₀ ) (meth) acrylic acid adduct is preferably 0.18 to 8.9 meq / g, more preferably 0.53 from the above viewpoint. -7.1 meq / g.
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 in (A2) is usually 500 to 3,000, preferably 1,000 to 2, from the viewpoint of developability as a photosensitive resin composition and photocuring reactivity when a (meth) acryloyl group is contained. 800, particularly preferably 1,500 to 2,500.

  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 whose SP values are close to each other are easy to mix with each other (high dispersibility), and those whose numerical values are apart from each other are indicators that 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 80%, more preferably 15 to 60%, particularly preferably 20 to 50% based on the solid content weight of (Q). contains.
If it is 10% or more, the developability can be further improved, and if it is 80% or less, the elastic recovery property of the cured product is further improved. In the present invention, “solid content” refers to components other than the solvent.

  In the present invention, the polyfunctional (meth) acrylate monomer (B) (hereinafter sometimes simply referred to as (B)) used as one component in the photosensitive resin composition is a known polyfunctional (meta) The acrylate monomer is not particularly limited, and examples thereof include 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 from the viewpoint of easily setting the difference from the SP value of (C) described later to -2.0 to 2.0. 9-12, especially 9.5-11.

  Among (B), preferred are (B2) and (B3), and more preferred is a polymer containing a hydroxyl group from the viewpoint of compatibility with (C) described later, particularly preferably dipentaerythritol pentaacrylate, Pentaerythritol triacrylate and combinations thereof. As (B) which can be easily obtained from the market, for example, Aronix M-403 (manufactured by Toagosei Co., Ltd.), light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.), neomer DA-600 (Sanyo Chemical Industries ( Etc.).

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 10 to 60%, more preferably 20 to 55%, and particularly preferably 25 to 52%. If it is 10% or more, the heat-resistant transparency of the cured product is further preferable, and if it is 60% or less, the developability is further improved.

In the present invention, the polysiloxane (C) having two or more hydrolyzable alkoxy groups contained as a component in the photosensitive resin composition (Q) is a silane compound (c1) represented by the general formula (1). It is a condensate in which a part of the alkoxy group [OR ³ in general formula (1)] is polymerized by condensation reaction as an essential constituent monomer.

In the formula, R ¹ is one or more selected from the group consisting of a (meth) acryloyloxyalkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group having 1 to 6 carbon atoms in the alkyl group. R ² is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 0 or 1. is there.

R ¹ does not react in the condensation reaction step (c1) but remains in the polysiloxane (C) after the condensation reaction, and contributes to the photocuring and / or heat curing of the photosensitive resin composition of the present invention. Functional group.
Preferred as R ¹ are a (meth) acryloyloxyalkyl group from the viewpoint of photocurability and a glycidoxyalkyl group from the viewpoint of thermosetting.

Among R ² , examples of the aliphatic saturated hydrocarbon group include a linear alkyl group, a branched alkyl group, and an alicyclic saturated hydrocarbon group.
Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-octyl and n-dodecyl groups and their deuterium substitutes, and examples of branched alkyl groups include isopropyl, isobutyl, sec-butyl and 2- Examples of the ethylhexyl group and the cyclic saturated hydrocarbon group include a cyclohexyl group, a cyclooctyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and a methylcyclohexyl group.
Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an alkylaryl group.
As aryl groups, phenyl, biphenyl, naphthyl groups and their deuterium, fluorine or chlorine substituents; As aralkyl groups, tolyl, xylyl, mesityl and their deuterium, fluorine or chloride; and as alkylaryl groups Examples include methylphenyl and ethylphenyl groups.
R ² is preferably a linear alkyl group, branched alkyl group and aryl group from the viewpoint of curing reactivity, more preferably a linear alkyl group and aryl group, particularly preferably a methyl group, an ethyl group, a phenyl group and These are combined.
Examples of R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group, and a methyl group and an ethyl group are preferable from the viewpoint of thermosetting reactivity. .

In the general formula (1), examples of the silane compound having a (meth) acryloyloxyalkyl group as R ¹ include the following compounds.
m is 0, that is, trifunctional silane compound having three alkoxy groups: 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3- Acryloyloxypropyltriethoxysilane and the like m is 1, that is, a trifunctional silane compound having two alkoxy groups: 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acrylic Leuoxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, etc.

Examples of the silane compound having a glycidoxyalkyl group as R ¹ include the following compounds.
m is 0, that is, trifunctional silane compound having 3 alkoxy groups, such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. m is 1, that is, 3 having 2 alkoxy groups Functional silane compounds: 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, etc.

Examples of the silane compound having a mercaptoalkyl group as R ¹ include the following compounds.
m is 0, that is, a trifunctional silane compound having three alkoxy groups, such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, etc. m is 1, that is, a trifunctional silane compound having two alkoxy groups. ..3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, etc.

Examples of the silane compound having an aminoalkyl group as R ¹ include the following compounds.
m is 0, that is, trifunctional silane compound having three alkoxy groups: N-2 aminoethyl γ-aminopropyltrimethoxysilane, N-2 aminoethyl γ-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, etc. m is 1, that is, a trifunctional silane compound having two alkoxy groups: N-2 aminoethyl γ-aminopropylmethyldimethoxysilane, N-2 aminoethyl γ-aminopropyl Methyldiethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, etc.

Of the silane compounds in which R ¹ has a (meth) acryloyloxyalkyl group or a glycidoxyalkyl group, a (meth) acryloyloxyalkyl group-containing trifunctional silane compound having three alkoxy groups, and A glycidoxyalkyl group-containing trifunctional silane compound having three alkoxy groups, particularly preferably 3-acryloyloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane.

Examples of (C) include a homocondensation polymer composed only of the silane compound (c1), and a cocondensate of one or more other silane compounds (c2) capable of cocondensing with (c1) and (c1). .
Examples of the other silane compound (c2) include a silane compound represented by the general formula (2).
R ² _n Si (OR ³ ) _4-n (2)
In the formula, R ² is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and n is 0 It is an integer of ~ 2.

Examples of R ² and R ³ include those exemplified above.
Among R ^2, a linear alkyl group, a branched alkyl group and an aryl group are preferable, a linear alkyl group and an aryl group are more preferable, and a methyl group, an ethyl group, a phenyl group and a combination thereof are particularly preferable.
R ³ is preferably a methyl group or an ethyl group.

In the general formula (2), examples of the tetrafunctional silane compound in which n is 0, that is, four alkoxy groups include tetramethoxysilane and tetraethoxysilane.
Examples of the trifunctional silane compound in which n is 1, that is, three alkoxy groups include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, and methyltriethoxysilane.
Examples of the bifunctional silane compound in which n is 2, that is, two alkoxy groups include diphenyldimethoxysilane, diphenyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldimethoxysilane, and phenylmethyldiethoxysilane. .
Of these, n is preferably 1, that is, a trifunctional silane compound from the viewpoint of forming a uniform network of polysiloxane (C).

  The charge ratio of the other silane compound (c2) is preferably from the viewpoint of light and / or thermosetting reactivity, and the total amount of the other silane compound (c2) is preferably 0.1 to 6.0 with respect to 1 mol of (c1). Mole, more preferably 0.2 to 4.0 mol is favorable.

  The polysiloxane (C) is, for example, 20 to 100 ° C. in a dry atmosphere with stirring a predetermined amount of water and, if necessary, the catalyst in the silane compound (c1) and other silane compound (c2) used as necessary. In about 10 minutes to 60 minutes, and then aged for 1 to 12 hours at a temperature below the boiling point of the by-produced alcohol (for example, 0 to 150 ° C.) to obtain a condensation reaction.

  When the amount of water added in the condensation reaction is X mol and the number of moles of alkoxy groups in the silane compound (c1) and the other silane compound (c2) is Y, if X / Y is too small, the yield of the condensate The molecular weight decreases. On the other hand, when X / Y is too large, the molecular weight becomes too large and the storage stability tends to decrease. From this, it is preferable to carry out in the range of 0.1 <X / Y <5, preferably in the range of 0.3 <X / Y <3. As the water to be added, ion exchange water or distilled water is usually used. Moreover, the silane compound which has one alkoxy group can also be added for the purpose of molecular weight adjustment. Examples of the silane compound having one alkoxy group include phenyltrimethoxysilane and methyltrimethoxysilane.

Condensation reaction catalysts include formic acid, acetic acid, succinic acid, lactic acid, malonic acid, citric acid, tartaric acid, malic acid, succinic acid, fumaric acid, phthalic acid, pyromellitic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoro Monovalent, divalent or trivalent organic acids such as acetic acid and trifluoromethanesulfonic acid; inorganic acids such as hydrochloric acid, phosphoric acid, nitric acid, hydrofluoric acid, bromic acid, chloric acid and perchloric acid; alkali metal hydroxides; Alkaline earth hydroxides, quaternary alkylammonium hydroxides and carbonates and alkali salts such as primary to tertiary amines; quaternary alkylammonium halides; sodium hypochlorite; tin, zirconium, titanium , Alkoxides of metals other than silicon such as aluminum and boron, and their chelate complexes; Organic acid among this, an inorganic acid, a metal alkoxide, an acid catalyst is preferable, chelate compounds of a metal alkoxide, an organic acid is particularly preferred.
The added amount of the catalyst is 0.0001 to 10 parts by weight, preferably 0.001 to 1 part by weight, based on 100 parts by weight of the total of (c1) and (c2). The method for adding the catalyst is not particularly limited, but is preferably added as an aqueous solution. Moreover, preferable reaction temperature is 20 to 100 degreeC.

  From the viewpoint of flatness, (C) preferably has a viscosity at 25 ° C. of 1 to 200 mPa · s, more preferably 1 to 100 mPa · s, and most preferably 1 to 50 mPa · s.

From the viewpoint of compatibility and heat-resistant transparency of the cured product, (C) preferably has a difference in SP value from the polyfunctional (meth) acrylate monomer (B) of −2.0 to 2.0, more preferably − It is 1.0 to 1.9, particularly preferably -0.5 to 1.8, and most preferably 0 to 1.7.
The SP value of (C) is preferably 7 to 13, more preferably 8 to 12, especially from the viewpoint that the difference from the SP value of (B) described above can be easily set to -2.0 to 2.0. 8-11, especially 8-10.5.

  The content of (C) based on the weight of the solid content of the photosensitive resin composition (Q) is preferably 1 to 50%, more preferably 3 to 40%, and particularly preferably 5 to 30%. If it is 5% or more, flatness and heat-resistant transparency can be exhibited more satisfactorily, and if it is 40% or less, compatibility can be exhibited more satisfactorily.

  Examples of the radical photopolymerization initiator (D) used as one component in the photosensitive resin composition (Q) include benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl. Propan-1-one, benzophenone, methylbenzoylformate, isopropylthioxanthone, 4,4-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone , Tert-butylanthraquinone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Cetophenone, 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, trimethylbenzoyldiphenylphosphine Sid, 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 10%, more preferably 0.05 to 7%, particularly preferably 0.1 to 57. %. If it is 0.01% or more, the photocuring reactivity can be exhibited more satisfactorily, and if it is 10% or less, the resolution can be further improved.

  In the photosensitive resin composition (Q), the content of (D) relative to the total weight of (A) in the case of having (B) and (meth) acryloyl groups is 0.02 to 20 from the viewpoint of photocurability. %, Preferably 0.05 to 10%.

The photosensitive resin composition (Q) may further contain other components (E) as necessary.
(E) includes inorganic fine particles (E1), sensitizer (E2), polymerization inhibitor (E3), solvent (E4), acid generator (E5), and other additives (E6) (for example, inorganic Pigments, silane coupling agents, dyes, fluorescent brighteners, yellowing inhibitors, antioxidants, antifoaming agents, deodorants, fragrances, bactericides, antibacterial agents, and fungicides.

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 etc.), aromatic hydrocarbons (eg anthracene and chrysene etc.), 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 the solvent, the same solvents as those used in the production of the above (A) can be used. When the solvent is used, the amount of the solvent is not particularly limited, but is preferably 50 to 1,000%, more preferably 70 to 900, based on the weight of the solid content of the photosensitive resin composition (Q). %, Particularly preferably 80 to 800%. In addition, the solvent used for manufacture of the above-mentioned (A) and (C) is also contained in the compounding quantity of a solvent.

The acid generator (E5) is a compound that generates an acid by light or heat, and is added to accelerate the condensation reaction of the alkoxy group.
Examples of (E5) include the following (i) sulfone compounds, (ii) sulfonic acid ester compounds, (iii) sulfonimide compounds, (iv) disulfonyldiazomethane (v) disulfonylmethane, and (vi) onium salts. .
(I) Sulfone compounds Phenacylphenylsulfone, 4-trisphenacylsulfone-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof (ii) Sulfonic acid ester compounds Benzoin tosylate, pyrogallol tristrifluoromethanesulfonate, pyrogallolmethane (Iii) sulfonimide compounds N- (trifluoromethylsulfonyloxy) succinimide, N- (p-toluenesulfonyloxy) bicyclo [2.2] sulfonic acid triester, α-methylolbenzointosylate, α-methylolbenzoindodecylsulfonate, etc. .1] Hept-5-ene-2,3-dicarboximide, N- (perfluorooctanesulfonyloxy) naphthylimide, N- (benzenesulfonyloxy) bishi [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (benzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-di Carboximide and N- (benzenesulfonyloxy) naphthylimide, etc. (iv) Disulfonyldiazomethane compounds Bis (trifluoromethylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (2,4 -Dimethylbenzenesulfonyl) diazomethane, bis (1-methylethylsulfonyl) diazomethane, bis (1,4-dioxaspiro [4,5] decane-7-sulfonyl) diazomethane, etc. (v) onium salts sulfonium salts [bis [4- ( Diphenylsulfonio) phenyl] sulfide bi Suhexafluorophosphate, allylsulfonium hexafluorophosphate salt, etc.)
Iodonium salts (such as diphenyliodonium hexafluorophosphate), phosphonium salts (such as ethyltriphenylphosphonium tetrafluoroborate), diazonium salts (such as phenyldiazonium hexafluorophosphate), ammonium salts (such as 1-benzyl-2-cyanopyridinium hexafluorophosphate) ), And ferrocene [(2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluorophosphate, etc.), etc.

  Of (E5), a sulfonimide compound and a disulfonyldiazomethane compound are preferable, and N- (trifluoromethylsulfonyloxy) succinimide and bis (phenylsulfonyl) diazomethane are more preferable.

  The content of (E5) based on the weight of the solid content of the photosensitive resin composition (Q) is preferably 10% or less, more preferably 0.01 to 7%, and particularly preferably 0.05 to 5%. . If it is 0.001% or more, the condensation reactivity of the hydrolyzable alkoxy group can be exhibited more satisfactorily, and if it is 10% or less, the heat-resistant transparency can be exhibited more favorably.

  The total content of (E) is usually 1,000% or less, preferably 80 to 800%, based on the weight of the photosensitive resin composition (Q).

The photosensitive resin composition (Q) of the present invention can be obtained, for example, by mixing the above-described components with a known mixing device such as a planetary mixer.
The photosensitive resin composition is usually liquid at room temperature, and its viscosity is 0.1 to 10,000 mPa · s, preferably 1 to 8,000 mPa · s at 25 ° C.

  The photosensitive resin composition (Q) of the present invention is particularly suitable as a photosensitive resin composition for a protective film for a color filter substrate because the cured product is excellent in heat-resistant transparency.

The protective film for a color filter substrate of the present invention will be described below.
The protective film for a color filter substrate of the present invention is a protective film provided for protecting a color filter formed by curing the photosensitive resin composition (Q) by a process including light irradiation.

A preferred formation step of the protective film for a color filter substrate of the present invention is a step of performing alkali development after light irradiation to form a pattern, and further performing post baking.
The formation of the protective film is usually performed in the following steps.

(1) The photosensitive resin composition of the present invention is applied onto a patterned glass substrate.
(2) Pre-drying.
(3) A negative film is adhered to the substrate.
(4) light irradiation step;
Polyfunctional (meth) acrylate monomer (B), hydrophilic polymer (A) when having (meth) acryloyl group, and polysiloxane having two or more hydrolyzable alkoxy groups when having (meth) acryloyl group The (meth) acryloyl group in (C) undergoes photocuring reaction.
(5) Alkaline development;
A pattern is formed.
(6) Post bake;
Thermally reactive group in polysiloxane (C) having two or more hydrolyzable alkoxy groups when R ¹ in formula (1) has a thermally reactive group (glycidyl group, mercapto group, amino group, etc.) And hydrolyzable alkoxy groups react with heat.

  As a method of applying and applying the protective film for the color filter substrate, there are a method of applying with a spin coater, slit coater, screen printing machine, roll coater, curtain coater, etc., a method of applying with a spray, a brush, a spatula, etc. Can be mentioned.

  The thickness of the protective film for the color filter substrate is usually 0.5 to 100 μm, preferably 1 to 10 μm.

  The preliminary drying is usually performed at 60 to 90 ° C. for 1 to 30 minutes.

  The following irradiation light sources are suitable for light irradiation. For example, there are a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halogen lamp, a laser (argon laser, dye laser, nitrogen laser, helium cadmium laser, etc.). Of these, high pressure mercury lamps and ultrahigh pressure mercury lamps are preferred.

  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%.

Alcohol-based organic solvents include aliphatic alcohols such as methanol, ethanol, n-propanol, i-propanol, and n-butanol), cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve, and carbitols such as methyl carbitol and ethyl carbitol Is mentioned.
The alcohol-based organic solvent is usually used at a concentration of 10 to 100%, preferably 20 to 50%.

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

As a heating device in the post-bake process, a normal air circulation dryer, an electric furnace, a gas furnace, a far infrared furnace, or the like 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 45 minutes to 90 minutes.

[Example]
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%).

[Production of compound (C) having two or more hydrolyzable alkoxy groups]
<Production Example C-1>
In a glass Kolben equipped with a heating / cooling / stirring measure, a reflux condenser, a dropping funnel and a nitrogen introduction pipe, 46 parts (0.2 mole part) 3-acryloyloxypropyltrimethoxysilane, 160 parts diphenyldimethoxysilane (0 .65 mol parts), 45 g (2.5 mol parts) of ion-exchanged water, and 0.1 part (0.001 mol parts) of oxalic acid, and heated and stirred at 60 ° C. for 6 hours. The methanol by-produced by hydrolysis was removed over 2 hours under reduced pressure of 50 mmHg. Thereafter, the solution is diluted with cyclohexanone so that the solid content is 25%, and a cyclohexanone solution of polysiloxane (C-1) (Mn: 2,100, viscosity: 20 mPa · s, SP value: 9.36) is obtained. (The solid content was 25%). The viscosity was measured using a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a constant temperature of 25 ° C. The same measurement method is used for the following production examples and comparative examples.

<Production Example C-2>
In the same Kolben as in Production Example C-1, 170 parts (0.82 mole part) of 3-glycidoxypropyltrimethoxysilane, 40 parts (0.20 mole part) of phenyltrimethoxysilane, 30 parts of diphenyldimethoxysilane ( 0.12 mol part), 40 g (2.2 mol parts) of ion-exchanged water, and 0.1 part (0.001 mol part) of oxalic acid, and heated and stirred under conditions of 60 ° C. for 6 hours, and further an evaporator. Was used to remove methanol by-produced by hydrolysis over 2 hours under reduced pressure of 50 mmHg. Thereafter, the solution is diluted with cyclohexanone so that the solid content is 25%, and a cyclohexanone solution of polysiloxane (C-2) (Mn: 7,800, viscosity: 70 mPa · s, SP value: 8.69) is obtained. (The solid content was 25%).

<Comparative Production Example C-1 ′>
In the same Kolben as in Production Example C-1, 46 parts (0.34 mole part) of methyltrimethoxysilane, 160 parts (0.80 mole part) of phenyltrimethoxysilane and 45 g (2.5 mole parts) of ion-exchanged water Then, 0.1 part (0.001 mol part) of oxalic acid was charged, heated and stirred under the conditions of 60 ° C. and 6 hours, and further by using an evaporator, methanol produced as a by-product by hydrolysis was reduced to 2 under a reduced pressure of 50 mmHg. Removed over time. Then, it was diluted with cyclohexanone so that the solid content was 25%, and cyclohexanone of comparative polysiloxane (C-1 ′) (Mn: 9,400, viscosity: 250 mPa · s, SP value: 8.49) A solution was obtained (solid content 25%).

<Comparative Production Example C-2 ′>
In the same Kolben as in Production Example C-1, 119 parts (1.14 mole part) of trimethylmonomethoxysilane, 45 g (2.5 mole part) of ion-exchanged water, and 0.1 part (0.001 mole part) of oxalic acid ), And heated and stirred at 60 ° C. for 6 hours. Further, by using an evaporator, methanol produced as a by-product by hydrolysis was removed under reduced pressure of 50 mmHg over 2 hours. Thereafter, the solution was diluted with cyclohexanone so that the solid content was 25%, and a cyclohexanone solution of comparative polysiloxane (C-2 ′) (Mn: 350, viscosity: 4 mPa · s, SP value: 6.75) was prepared. Obtained (solid content 25%).

<Examples 1-6 and Comparative Examples 1-4>
[Production of photosensitive resin composition]
Number of blended parts in Table 1 [apparent parts by weight of each component, () indicates the weight% of the solid content of each component based on the weight of the solid content of the photosensitive resin composition (Q) (one decimal place) The raw materials are charged in a glass container and stirred until uniform, and an additional solvent (propylene glycol monomethyl ether acetate) is added to the photosensitive resin compositions (Q1) to (Q1) to (Example). Q6) and the photosensitive resin compositions (Y1) to (Y5) of Comparative Examples were produced. The abbreviations in Table 1 other than the above are as follows.

B-1 (polyfunctional (meth) acrylate): “light acrylate PE-3A” (SP value: 10.30, pentaerythritol triacrylate: manufactured by Kyoeisha Chemical Co., Ltd.),
C-3 ′: One-terminal glycidyl group-modified polysiloxane (“X-22-173DX”: manufactured by Shin-Etsu Chemical Co., Ltd.) (viscosity: 65 mPa · s, SP value: 6.66)
D-1 (photo radical polymerization initiator): “Irgacure 907” (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one: manufactured by Ciba Specialty Chemicals Co., Ltd. ),
E-1 (photoacid generator): N- (trifluoromethylsulfonyloxy) succinimide

評価方法および評価結果
（１）現像性・・・感光性樹脂組成物（Ｑ１）〜（Ｑ６）、および（Ｙ１）〜（Ｙ５）を、それぞれガラス基板上に仕上り膜厚が５μｍになるようにスピンコートし、２５℃で５分間乾燥し、高圧水銀灯を用い露光量１００ｍＪので露光後、その後１％炭酸ナトリウム水溶液を用いて３０秒間現像を行い、現像性を評価した。結果を表１に示す。評価基準は以下の通りである。
◎：目視により残留物無し。
○：目視により残留物わずかにあり。
△：目視により残留物が多い。

Evaluation Method and Evaluation Results (1) Developability: photosensitive resin compositions (Q1) to (Q6) and (Y1) to (Y5) are each finished on a glass substrate so that the finished film thickness is 5 μm. The film was spin-coated, dried at 25 ° C. for 5 minutes, exposed using a high-pressure mercury lamp at an exposure amount of 100 mJ, and then developed using a 1% aqueous sodium carbonate solution for 30 seconds to evaluate the developability. The results are shown in Table 1. 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) Coating film performance: The photosensitive resin composition was applied on the entire surface of the patterned glass substrate and dried at 80 ° C. for 20 minutes. Next, a negative film was brought into close contact with this substrate, exposed using a high pressure mercury lamp at an exposure amount of 100 mJ, and developed with a 1% aqueous sodium carbonate solution to form a pattern. Next, this substrate was thermally cured at 150 ° C. for 60 minutes to prepare an evaluation substrate having a cured coating film, and the total light transmittance of the evaluation substrate and the heat-resistant transparency after the heat treatment of the evaluation substrate were evaluated.

(A) Total light transmittance: Measured according to JIS K7105 (1981) using a haze meter [manufactured by Nippon Denshoku Industries Co., Ltd.] using a 2 mm thick, 40 mm square test plate.

(B) Heat-resistant transparency: An evaluation substrate having a cured coating film was heat-treated at 250 ° C. for 1 hr, and the transmittance of light having wavelengths of 400 nm and 540 nm was measured.
(Transmissivity meter: UV2400PC manufactured by Shimadzu Corporation)

(C) Flatness: The thickness of the surface of the protective film was measured using a stylus type film thickness meter (DEKTAK3030ST) (measurement length: 1000 μm), and the flattening rate was determined by the following formula.
Flattening rate (%) = B / A × 100
A ... (maximum film thickness value-minimum film thickness value) μm (before protective film formation)
B ... (maximum film thickness value-minimum film thickness value) μm (after protective film formation)

  As can be seen from Tables 1 and 2, by using the photosensitive resin composition of the present invention, a color filter substrate 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 the protective film for color filter substrates.
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, coating agents for various materials such as metals (for example, iron, aluminum, titanium, copper, etc.), plastics (for example, polycarbonate, polyethylene terephthalate, poly (meth) acrylate), paper, glass, rubber and wood, paints, It can also be used as a printing ink and an adhesive, and can also be applied as a molding material.

Claims (7)

Containing a hydrophilic polymer (A), a polyfunctional (meth) acrylate monomer (B), a polysiloxane (C) having two or more hydrolyzable alkoxy groups, and a photoradical polymerization initiator (D), A photosensitive resin composition (Q) for a color filter substrate protective film, wherein (C) is a condensate containing a silane compound (c1) represented by the following general formula (1) as an essential constituent monomer.

[Wherein, R ¹ is one selected from the group consisting of a (meth) acryloyloxyalkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group, wherein the alkyl group has 1 to 6 carbon atoms. The above organic group, R ² is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and m is 0 or 1 It is. ] The photosensitive resin composition (Q) according to claim 1, wherein (c1) is a silane compound in which R ¹ in the general formula (1) is a (meth) acryloyloxyalkyl group. The thermosetting resin composition (Q) according to claim 1 or 2, wherein the polysiloxane (C) has a viscosity of 1 to 200 mPa · s at 25 ° C. The difference in solubility parameter between the polyfunctional (meth) acrylate monomer (B) and the compound (C) having two or more hydrolyzable alkoxy groups is -2.0 to 2.0. The photosensitive resin composition (Q) described. 5. The photosensitive resin composition according to claim 1, wherein the content of the polysiloxane (C) is 5 to 30% by weight based on the weight of the solid content of the thermosetting resin composition (Q). Q). A protective film provided for protecting a color filter, which is formed by curing the photosensitive resin composition according to claim 1 through a process including light irradiation. The protective film according to claim 6, wherein the step including light irradiation is a step in which after light irradiation, alkali development is performed to form a pattern, and further post-baking is performed.