Modified polyol compound and photosensitive resin composition

Abstract

To provide a photosensitive resin composition that exhibits good developability and provides a resin cured film with favorable adhesion and favorable solvent resistance.SOLUTION: A modified polyol compound in which a part of hydroxyl groups possessed by a polyol compound is modified into a structure having an ethylenically unsaturated group, the polyol compound having two or more aromatic rings, and at least one of the aromatic rings taking one or more structures selected from the group consisting of a catechol structure and a pyrogallol structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a modified polyol compound, a photosensitive resin composition, a cured resin film, a photosensitive colored composition, a color filter, and an image display element. [Background technology]

[0002] Currently, from the viewpoint of resource and energy conservation, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams are widely used in the fields of various coatings, printing, paints, adhesives, etc. In the field of electronic materials, photosensitive resin compositions are used as solder resists for printed wiring boards and the like, and color filter resists for displays such as liquid crystal and organic EL displays.

[0003] In recent years, photosensitive resin compositions have been proposed that have low-temperature curing properties and are compatible with components with low heat resistance, such as organic electroluminescence (EL) devices. For example, Patent Document 1 discloses an alkali-soluble resin that can give a cured product that has excellent solvent resistance and adhesion to substrates even under low-temperature curing conditions and that can be suitably used in applications such as color filters. The alkali-soluble resin has a structural unit (A) derived from an oxetanyl group-containing monomer, a structural unit (B) derived from an acid anhydride monomer, and a structural unit (C) derived from an acid group-containing compound adduct of a hydroxyl group-containing monomer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-14542 Summary of the Invention [Problem to be solved by the invention]

[0005] These photosensitive resin compositions are required to have curability that allows them to cure well under low temperature conditions without causing curing failure, and good adhesion that prevents the cured product from leaching or peeling from the substrate even when exposed to various solvents in the subsequent manufacturing process. Patent Document 1 describes how hydroxyl groups, which contribute to low-temperature curing, are capped with acid anhydrides to prevent them from crosslinking before the curing process, and then the acid anhydrides are eliminated by heating to form hydroxyl groups, thereby achieving low-temperature curing. However, this method raises concerns that the eliminated acid anhydrides may become liberated, adversely affecting the curing properties and the adhesion of the cured product.

[0006] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a modified polyol compound that is suitable for use in a photosensitive resin composition. Another object of the present invention is to provide a photosensitive resin composition that has good developability and gives a cured resin film with good adhesion and solvent resistance. Another object of the present invention is to provide an image display element that includes a cured resin film with excellent adhesion and solvent resistance, and a cured product of a photosensitive coloring composition that contains a photosensitive resin composition and a colorant. [Means for solving the problem]

[0007] The present invention includes the following aspects. [1] A part of the hydroxy groups of the polyol compound is modified to a structure having an ethylenically unsaturated group, The polyol compound has two or more aromatic rings, and at least one of the aromatic rings has one or more structures selected from a catechol structure and a pyrogallol structure. [2] The modified polyol compound according to [1], wherein the polyol compound is one or more selected from the group consisting of luteolin, taxifolin, myricetin, quercetin, rutin, catechin, epigallocatechin gallate, butein, piceatannol, and tannic acid. [3] The modified polyol compound according to [1] or [2], wherein the structure having an ethylenically unsaturated group is a structure having one or more groups selected from the group consisting of a (meth)acryloyloxy group and a vinyloxy group. [4] The modified polyol compound according to any one of [1] to [3], wherein a polybasic acid or an anhydride thereof is further added to a portion of the hydroxy groups of the polyol compound. [5] The modified polyol compound according to any one of [1] to [4], which has a hydroxyl value of 30 to 900 mgKOH / g. [6] The modified polyol compound according to any one of [1] to [5], which has an ethylenically unsaturated group equivalent of 50 to 900 g / mol. [7] The modified polyol compound according to [4], wherein the modification rate of the hydroxy groups of the polyol compound is 5 to 90%. [8] (A) an alkali-soluble resin; (B) a reactive diluent; (C) a photopolymerization initiator; (D) a solvent; (E) a modified polyol compound according to any one of [1] to [7]; A photosensitive resin composition comprising: [9] With respect to 100 parts by mass of the total of (A), (B), (C), and (E), The (A) alkali-soluble resin is contained in an amount of 10 parts by mass to 70 parts by mass, The (B) reactive diluent is contained in an amount of 5 parts by mass to 50 parts by mass, The (C) photopolymerization initiator is contained in an amount of 0.1 to 10 parts by mass, The (D) solvent is contained in an amount of 30 parts by mass to 1000 parts by mass, The (E) modified polyol compound is contained in an amount of 0.05 parts by mass to 50 parts by mass. [8] The photosensitive resin composition according to [8].

[10] A cured resin film comprising a cured product of the photosensitive resin composition according to [8] or [9].

[11] A photosensitive coloring composition comprising the photosensitive resin composition according to [8] or [9] and (F) a colorant.

[12] A cured resin film comprising a cured product of the photosensitive coloring composition according to

[11] .

[13] A color filter having a color pattern made of a cured product of the photosensitive coloring composition according to

[11] .

[14]

[13] An image display device comprising the color filter according to

[13] . [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a modified polyol compound that improves the developability of a photosensitive resin composition and the adhesion and solvent resistance of the cured product thereof. Furthermore, it is possible to provide a photosensitive resin composition that has good developability and gives a cured resin film with good adhesion and solvent resistance. Furthermore, it is possible to provide an image display element that includes a cured resin film with excellent adhesion and solvent resistance obtained by curing the photosensitive resin composition, and a cured product of a photosensitive coloring composition containing the photosensitive resin composition and a colorant. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the embodiments described below.

[0010] In this specification, "(meth)acrylic" means acrylic or methacrylic, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy.

[0011] In this specification, the hydroxyl value is a value measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K0070:1992.

[0012] In this specification, the acid value of the modified polyol compound means the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the modified polyol compound according to JIS K 0070:1992.

[0013] In this specification, the ethylenically unsaturated group equivalent is a value calculated from the amounts of raw materials charged.

[0014] In this specification, the acid value of the solid content of (A) alkali-soluble resin is a value measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K6901:2008 5.3. The acid value of the solid content of (A) alkali-soluble resin means the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of (A) alkali-soluble resin.

[0015] In this specification, the weight average molecular weight refers to a weight average molecular weight measured using gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene. Column: Showdex (registered trademark) Two LF-804 (manufactured by Showa Denko K.K.) columns were connected in series. Column temperature: 40℃ Sample: 0.2% by mass solution of the object to be measured in tetrahydrofuran Developing solvent: tetrahydrofuran Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko K.K.) Flow rate: 1mL / min

[0016] <Modified polyol compounds> In one embodiment, the modified polyol compound is a compound in which some of the hydroxy groups of a polyol compound have been modified to a structure having an ethylenically unsaturated group. The polyol compound has two or more aromatic rings, and at least one of the aromatic rings has one or more structures selected from a catechol structure and a pyrogallol structure. The modified polyol compound may further have a polybasic acid or an anhydride thereof added to some of the hydroxy groups of the polyol compound, as necessary.

[0017] [Polyol compounds] The polyol compound is not particularly limited as long as it is a compound having multiple hydroxy groups and two or more aromatic rings, and at least one of the aromatic rings has one or more structures selected from a catechol structure and a pyrogallol structure. The catechol structure is a structure in which two hydroxy groups are bonded to a benzene ring, and the pyrogallol structure is a structure in which three hydroxy groups are bonded to a benzene ring. Therefore, the polyol compound is a compound having at least one group selected from a 2,3-dihydroxyphenyl group, a 3,4-dihydroxyphenyl group, a 2,3,4-trihydroxyphenyl group, and a 3,4,5-trihydroxyphenyl group.

[0018] Specific examples of polyol compounds include luteolin, taxifolin, myricetin, quercetin, rutin, catechin, epigallocatechin gallate, butein, piceatannol, and tannic acid. Among them, myricetin, catechin, and tannic acid are preferred because they provide good developability and good solvent resistance of the cured product when used in a photosensitive resin composition described below. In particular, compounds having four or more phenolic hydroxyl groups are preferred from the viewpoints of improving the storage stability of the photosensitive resin composition by suppressing the increase in molecular weight of the alkali-soluble resin (A) described below, improving the adhesion of the cured product, and inhibiting polymerization or reaction in the formulation. In addition, tannic acid is more preferred because it has a high molecular weight and can be used as a polymer substitute.

[0019] The polyol compounds may be used alone or in combination of two or more kinds.

[0020] [Modified polyol compounds] The modified polyol compound is a compound in which at least a portion of the hydroxy groups of a polyol compound has been modified to a structure having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth)acryloyl group. Among these, from the viewpoint of photocurability as a photosensitive resin composition, a vinyl group and a (meth)acryloyl group are preferred, and a (meth)acryloyl group is more preferred. As the structure having an ethylenically unsaturated group, a structure having one or more selected from the group consisting of a (meth)acryloyloxy group and a vinyloxy group (CH2=CH-O-: vinyl ether group) is preferred, a (meth)acryloyloxy group and a vinyloxy group are more preferred, and a (meth)acryloyloxy group is even more preferred.

[0021] The hydroxyl value of the modified polyol compound is preferably 30 to 900 mgKOH / g, more preferably 60 to 800 mgKOH / g, and even more preferably 100 to 700 mgKOH / g. When the hydroxyl value is 30 mgKOH / g or more, the development speed and pattern shape are good when used as a photosensitive resin composition. When the hydroxyl value is 900 mgKOH / g or less, the fine line adhesion is good when used as a photosensitive resin composition.

[0022] The ethylenically unsaturated group equivalent of the modified polyol compound is preferably 50 to 900 g / mol, more preferably 100 to 800 g / mol, and even more preferably 200 to 700 g / mol. When the ethylenically unsaturated group equivalent is 50 g / mol or more, the storage stability and development characteristics are good when used as a photosensitive resin composition. When the ethylenically unsaturated group equivalent is 900 g / mol or less, the fine line adhesion and solvent resistance of the cured product are good when used as a photosensitive resin composition.

[0023] The modification rate of the hydroxy groups in the polyol compound is preferably 5 to 90%, more preferably 10 to 80%, and even more preferably 20 to 70%. When the modification rate is 5% or more, the solvent resistance is good when used as a photosensitive resin composition. When the modification rate is 90% or less, the development speed is good when used as a photosensitive resin composition. In this specification, the modification rate of the hydroxy groups in the polyol compound is a value calculated from the charge ratio of the compound to be added to the hydroxy groups in the polyol compound (for example, a compound having an isocyanato group and an ethylenically unsaturated group, a compound having an epoxy group and an ethylenically unsaturated group, and a polybasic acid or anhydride thereof), assuming a reaction rate of 100%.

[0024] The acid value of the modified polyol compound is preferably 0 to 200 mgKOH / g, more preferably 0 to 150 mgKOH / g, and even more preferably 0 to 120 mgKOH / g. Even when the acid value is 0 mgKOH / g, development using phenolic hydroxyl groups is possible. When the acid value is 200 mgKOH / g or less, fine line adhesion is good. From the viewpoint of improving developability, the lower limit of the acid value may be 5 mgKOH / g, 10 mgKOH / g, or 50 mgKOH / g.

[0025] (Method for modifying polyol compound) Examples of methods for modifying a polyol compound include a method of reacting a compound having an isocyanato group and an ethylenically unsaturated group with a hydroxy group of a polyol compound in the presence of a solvent and a catalyst, and a method of reacting a compound having an epoxy group and an ethylenically unsaturated group with a hydroxy group of a polyol compound. These reactions are usually carried out under conditions of 70°C to 130°C, preferably for 30 minutes to 10 hours, more preferably for 1 to 6 hours.

[0026] <Compound having an isocyanato group and an ethylenically unsaturated group> The compound having an isocyanato group and an ethylenically unsaturated group is not particularly limited as long as it is a compound having an isocyanato group and an ethylenically unsaturated group, and examples thereof include compounds represented by the following formula (XX1):

[0027] [ka]

[0028] In formula (XX1), R 11 represents a hydrogen atom or a methyl group, and R 12 -CO-, -COOR 13 -(where R 13 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 14 O-CONH-R 15 -(where R 14 is an alkylene group having 2 to 6 carbon atoms, and R 15 represents an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent. 12 is preferably -COOR 13 -, where R 13 is preferably an alkylene group having 1 to 4 carbon atoms.

[0029] Specific examples of the compound represented by formula (XX1) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate.

[0030] The compound having an isocyanato group and an ethylenically unsaturated group may also be an equimolar (1 mol:1 mol) reaction product of a hydroxyalkyl (meth)acrylate and a diisocyanate compound. The alkyl group of the hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group. Examples of diisocyanate compounds include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4-) bis(isocyanatomethyl)cyclohexane, and lysine diisocyanate.

[0031] Among these, from the viewpoints of ease of the modification reaction and photocurability when used as a photosensitive resin composition, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.

[0032] The compound having an isocyanato group and an ethylenically unsaturated group may be used alone or in combination of two or more kinds.

[0033] <Compound having an epoxy group and an ethylenically unsaturated group> The compound having an epoxy group and an ethylenically unsaturated group is not particularly limited as long as it is a compound having an epoxy group and an ethylenically unsaturated group. Specific examples include (meth)acrylates having an alicyclic epoxy group, such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate, mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, and epoxidized dicyclopentenyloxyethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoints of ease of modification reaction and photocurability when used as a photosensitive resin composition.

[0034] The compound having an epoxy group and an ethylenically unsaturated group may be used alone or in combination of two or more kinds.

[0035] <Solvent> The solvent is not particularly limited as long as it does not react with the components and can dissolve or disperse the components. Specific examples of the solvent include the same solvents as the (D) solvent used in the photosensitive resin composition described below.

[0036] Catalyst The catalyst is not particularly limited, but examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine and tri(p-tolyl)phosphine, metal chelate compounds containing metals such as chromium and lithium, and tin compounds such as tin 2-ethylhexanoate and dibutyltin dilaurate (DBTDL).

[0037] <Polymerization inhibitor> When carrying out the modification reaction, a polymerization inhibitor other than the polyol compound and the modified polyol compound may be added to the reaction solution as needed to prevent gelation of the reaction solution. However, since the polyol compound and the modified polyol compound have a phenolic hydroxyl group and have a polymerization inhibitory effect, it is usually not necessary to add another polymerization inhibitor. The other polymerization inhibitor is not particularly limited, but examples include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene. From the viewpoint of minimizing the effect on the physical properties when used as a photosensitive resin composition, it is preferable not to use another polymerization inhibitor.

[0038] (Addition reaction of polybasic acids or their anhydrides) When a polybasic acid or anhydride thereof is to be added to some of the remaining hydroxy groups after the modification reaction of a polyol compound, the polybasic acid or anhydride thereof, and optionally a catalyst, can be added to the reaction solution after the modification reaction to carry out the addition reaction. The addition reaction is usually carried out under conditions of 70°C to 130°C, preferably for 30 minutes to 5 hours, more preferably for 1 to 3 hours.

[0039] <Polybasic acid or anhydride thereof> The polybasic acid or anhydride thereof is a compound having two or more carboxy groups or anhydride thereof. Examples of polybasic acids include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. Examples of polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, and octenylsuccinic anhydride. Among these, polybasic acid anhydrides are preferred from the viewpoint of reactivity with hydroxy groups, and 1,2,3,6-tetrahydrophthalic anhydride is more preferred.

[0040] The polybasic acids or anhydrides thereof may be used alone or in combination of two or more kinds.

[0041] Catalyst Specific examples of the catalyst include the same catalysts as those used in the modification reaction of the polyol compound. The catalyst used in the modification reaction of the polyol compound may be used as is, or a new catalyst may be added.

[0042] <Photosensitive resin composition> The photosensitive resin composition of one embodiment contains (A) an alkali-soluble resin, (B) a reactive diluent, (C) a photopolymerization initiator, (D) a solvent, and (E) a modified polyol compound.

[0043] [(A) Alkali-soluble resin] The alkali-soluble resin (A) is not particularly limited as long as it is an alkali-soluble resin that does not fall under the category of the modified polyol compound (E), and any known alkali-soluble resin that is commonly used can be used without limitation. The alkali-soluble resin (A) may be used alone or in combination of two or more kinds.

[0044] The acid value of the solid content of the (A) alkali-soluble resin is preferably 10 to 300 mgKOH / g, more preferably 20 to 200 mgKOH / g, and even more preferably 30 to 150 mgKOH / g, from the viewpoint of improving the developability when developing the photosensitive resin composition after exposure. When the acid value of the solid content is 10 mgKOH / g or more, the alkali solubility of the photosensitive resin composition is sufficient, and therefore good developability can be obtained. When the acid value of the solid content is 300 mgKOH / g or less, the storage stability of the photosensitive resin composition is good.

[0045] The weight-average molecular weight of the (A) alkali-soluble resin is preferably 1000 to 50000, more preferably 3000 to 30000, and even more preferably 5000 to 20000. When the weight-average molecular weight is within this range, the viscosity of the photosensitive resin composition can be easily controlled, and good storage stability can be obtained.

[0046] The alkali-soluble resin (A) preferably has an ethylenically unsaturated group introduced therein, since this is expected to maximize the effect of improving the photocurability of the photosensitive resin composition.

[0047] When the (A) alkali-soluble resin has an ethylenically unsaturated group, the ethylenically unsaturated group equivalent is preferably 100 to 3,000 g / mol, more preferably 150 to 2,500 g / mol, and even more preferably 200 to 2,000 g / mol. When the ethylenically unsaturated group equivalent is 100 g / mol or more, the photosensitive resin composition has good storage stability. When the ethylenically unsaturated group equivalent is 3,000 g / mol or less, the photosensitive resin composition has good curability, and therefore the cured product has good solvent resistance.

[0048] As the alkali-soluble resin (A), it is preferable to use a (meth)acrylic resin or an epoxy (meth)acrylate resin from the viewpoint of the performance of the cured product, such as fine line adhesion, solvent resistance, and pattern formability.

[0049] [Epoxy (meth)acrylate resin] Epoxy (meth)acrylate resin is a resin in which an unsaturated monobasic acid such as (meth)acrylic acid is added to an epoxy compound.

[0050] (epoxy compounds) As the epoxy compound, a known epoxy compound can be appropriately selected and used. As the epoxy compound, a compound obtained by reacting a compound having a phenolic hydroxyl group with epihalohydrin can also be used. As the compound having a phenolic hydroxyl group, a compound having two or more phenolic hydroxyl groups is preferred, and it may be a monomer or a polymer. As the epihalohydrin, epichlorohydrin is preferably used. Specific examples of epoxy compounds include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, biphenyl novolac type epoxy compounds, trisphenolmethane type epoxy compounds, epoxidized products of copolymers of phenol and dicyclopentadiene, and diglycidyl ethers of 1,1-bis(4'-hydroxyphenyl)adamantane. As with these specific examples, epoxy compounds having an aromatic ring in the main chain can be preferably used. Among these, from the viewpoint of high cured film strength, bisphenol A type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, and epoxidized products of copolymers of phenol and dicyclopentadiene are preferred.

[0051] Specific examples of the epoxy compound include bisphenol A type epoxy compounds (e.g., jER (registered trademark, the same applies hereinafter) 828, jER1001, jER1002, jER1004 manufactured by Mitsubishi Chemical Corporation, and NER-1302 (epoxy equivalent: 323, softening point: 76°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type compounds (e.g., jER807, jER4004P, jER4005P, jER4007P manufactured by Mitsubishi Chemical Corporation, and NER-7406 (epoxy equivalent: 350, softening point: 66°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy compounds, biphenyl diglycidyl ether (e.g., jERYX-4000 manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy compounds (e.g., EPPN (registered trademark, the same applies hereinafter)-201 manufactured by Nippon Kayaku Co., Ltd., and jER 152, jER154, DEN-438, EOCN-104S, etc., manufactured by The Dow Chemical Company), triglycidyl isocyanurate (for example, TEPIC (registered trademark) manufactured by Nissan Chemical Industries, Ltd.), (o, m, p-) cresol novolac type epoxy resin (for example, EOCN (registered trademark, the same applies hereinafter)-102S, EOCN-1020, etc., manufactured by Nippon Kayaku Co., Ltd.), alicyclic epoxy compounds (for example, CELLOXIDE (registered trademark, the same applies hereinafter) 2021P, CELLOXIDE EHPE, etc., manufactured by Daicel Corporation), trisphenolmethane type epoxy compounds (for example, EPPN-501, EPPN-502, EPPN-503, NC-7300, XD-1000, NC-3000, etc., manufactured by Nippon Kayaku Co., Ltd.), epoxidized copolymers of dicyclopentadiene and phenol (for example, EXA-7200, etc., manufactured by DIC Corporation).

[0052] (unsaturated monobasic acid) The unsaturated monobasic acid can be appropriately selected from known unsaturated monobasic acids, and specific examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, and cinnamic acid.

[0053] [(Meth)acrylic resin] As the (meth)acrylic resin, it is preferable to use a (meth)acrylic resin into which an ethylenically unsaturated group has been introduced, from the viewpoints of low-temperature curing properties and adhesion of the cured product.

[0054] The (meth)acrylic resin having an ethylenically unsaturated group introduced therein is preferably a (meth)acrylic resin selected from the following: (Meth)acrylic resin (1): An adduct of an ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group to a (meth)acrylic copolymer containing a structural unit (ma-1) derived from an ethylenically unsaturated group-containing compound (m-1) having a carboxy group. (Meth)acrylic resin (2): an adduct of a compound having an alkali-soluble functional group to an adduct of an ethylenically unsaturated group-containing compound (a-2) having a carboxy group to a (meth)acrylic copolymer containing a structural unit (ma-2) derived from an ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group.

[0055] (Meth)acrylic resin (1) The (meth)acrylic resin (1) is a (meth)acrylic resin in which an ethylenically unsaturated group is introduced by adding an ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group to a (meth)acrylic copolymer containing a structural unit (ma-1) derived from an ethylenically unsaturated group-containing compound (m-1) having a carboxy group, and optionally a structural unit (ma-3) other than the structural unit (ma-1) derived from another monomer (m-3).

[0056] <Ethylenically unsaturated group-containing compound (m-1) having a carboxy group> The ethylenically unsaturated group-containing compound (m-1) having a carboxy group is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a carboxy group in one molecule. Among them, (meth)acrylic acid and its derivatives, and compounds having a (meth)acryloyloxy group and a carboxy group are preferred. Specific examples of the ethylenically unsaturated group-containing compound (m-1) having a carboxy group include (meth)acrylic acid; compounds having a (meth)acryloyloxy group and a carboxy group, such as 2-(meth)acryloyloxyethyl succinic acid and 2-(meth)acryloyloxyethyl hexahydrophthalic acid; derivatives of (meth)acrylic acid, such as α-bromo(meth)acrylic acid and β-furyl(meth)acrylic acid; crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, and monoethyl itaconate. The ethylenically unsaturated group-containing compound (m-1) having a carboxy group may be used alone or in combination of two or more kinds.

[0057] Other Monomers (m-3) The other monomer (m-3) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, or an oxetanyl group and is copolymerizable with the ethylenically unsaturated group-containing compound (m-1) that has a carboxy group.

[0058] Other monomers (m-3) include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate; adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, and cyclohexyl ( (Meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, such as methyl (meth)acrylate; hydroxyalkyl (meth)acrylates, such as hydroxyethyl (meth)acrylate; phenyl (meth)acrylate, triphenylmethyl (meth)acrylate, naphthyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, anthracene (meth)acrylate, benzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate aromatic hydrocarbon group-containing (meth)acrylates such as 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, and perfluoroisopropyl (meth)acrylate; conjugated diene compounds such as butadiene, isoprene, and chloroprene; (meth)acrylic acid ester compounds such as 3-(N,N-dimethylamino)propyl (meth)acrylate, cumyl (meth)acrylate, isoamyl acrylate, methoxytriethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate (for example, trade name: AM-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.), phenoxyethyl acrylate, and phenoxypolyethylene glycol acrylate (for example, trade name: LightAcrylate P-200A, manufactured by Kyoeisha Chemical Co., Ltd.);Examples of (meth)acrylic acid amide compounds include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide; (meth)acrylonitrile; vinyl compounds such as acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diester compounds such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide; styrene; and styrene derivatives such as α-, o-, m-, and p-alkyl derivatives of styrene. Among these, from the viewpoints of development characteristics, curability, and solvent resistance of the cured product, (meth)acrylates containing an alicyclic hydrocarbon group having 6 to 20 carbon atoms, alkyl (meth)acrylates, (meth)acrylates containing an aromatic hydrocarbon group, and styrene are preferred, and benzyl (meth)acrylate, tricyclodecanyl (meth)acrylate, and styrene are more preferred. The other monomers (m-3) may be used alone or in combination of two or more.

[0059] <Ethylenically Unsaturated Group-Containing Compound (a-1) Having an Epoxy Group or an Oxetanyl Group> The ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples of the ethylenically unsaturated group-containing compound having an epoxy group include epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer (registered trademark) A200 and M100 manufactured by Daicel Corporation), mono(meth)acrylic acid ester of 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, and epoxidized dicyclopentenyloxyethyl (meth)acrylate. Specific examples of ethylenically unsaturated group-containing compounds having an oxetanyl group include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetane. Among these, epoxy group-containing (meth)acrylates are preferred, and glycidyl (meth)acrylate is more preferred. The ethylenically unsaturated group-containing compounds (a-1) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0060] <Proportion of structural units of (meth)acrylic resin (1)>

[0061] The carboxyl group-containing ethylenically unsaturated group-containing compound (m-1) preferably accounts for 10 to 80 mol %, more preferably 15 to 70 mol %, and even more preferably 20 to 60 mol % of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (1). When the carboxyl group-containing ethylenically unsaturated group-containing compound (m-1) is 10 mol % or more, alkaline developability is good. When the carboxyl group-containing ethylenically unsaturated group-containing compound (m-1) is 80 mol % or less, fine line adhesion and storage stability are good.

[0062] The other monomer (m-3) is preferably 20 to 90 mol%, more preferably 30 to 85 mol%, and even more preferably 40 to 80 mol% of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (1). When the other monomer (m-3) is 20 mol% or more, storage stability is good. When the other monomer (m-3) is 90 mol% or less, sufficient alkali developability and adhesion are obtained.

[0063] The amount of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is preferably 5 to 80 moles, more preferably 10 to 70 moles, and even more preferably 20 to 60 moles, relative to a total of 100 moles of functional groups reactive with epoxy groups or oxetanyl groups possessed by the monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (1). When the amount of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is 5 moles or more, good curability is achieved. When the amount of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group is 80 moles or less, good fine wire adhesion and storage stability are achieved.

[0064] (Meth)acrylic resin (2) The (meth)acrylic resin (2) is a (meth)acrylic resin obtained by adding a carboxyl group-containing ethylenically unsaturated group-containing compound (a-2) to a (meth)acrylic copolymer containing a structural unit (ma-2) derived from an ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group, and optionally a structural unit (ma-4) other than the structural unit (ma-2) derived from another monomer (m-4), to introduce an ethylenically unsaturated group, and further adding a compound having an alkali-soluble functional group to introduce an alkali-soluble functional group. The compound having an alkali-soluble functional group is preferably a polybasic acid or polybasic acid anhydride (a-3). The compound having an alkali-soluble functional group can be added to the functional group of the (meth)acrylic copolymer having the above-mentioned ethylenically unsaturated group, and a specific example thereof is a hydroxy group.

[0065] <Ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group> The ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group is not particularly limited as long as it does not have a carboxy group and has an ethylenically unsaturated group and an epoxy group or an oxetanyl group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (a-1) having an epoxy group or an oxetanyl group. The ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group may be used alone or in combination of two or more.

[0066] <Other Monomers (m-4)> The other monomer (m-4) is not particularly limited as long as it is a monomer that does not have a carboxy group, an epoxy group, or an oxetanyl group and is copolymerizable with the ethylenically unsaturated group-containing compound (m-2) that has an epoxy group or an oxetanyl group. Specific examples and preferred examples are the same as those of the other monomer (m-3). The other monomer (m-4) may be used alone or in combination of two or more.

[0067] <Ethylenically Unsaturated Group-Containing Compound (a-2) Having a Carboxy Group> The ethylenically unsaturated group-containing compound (a-2) having a carboxy group is not particularly limited as long as it is a compound having an ethylenically unsaturated group and a carboxy group in one molecule. Specific examples and preferred examples are the same as those of the ethylenically unsaturated group-containing compound (m-1) having a carboxy group. The ethylenically unsaturated group-containing compound (a-2) having a carboxy group may be used alone or in combination of two or more.

[0068] <Polybasic acid or polybasic acid anhydride (a-3)> By adding a polybasic acid or polybasic acid anhydride (a-3) to the (meth)acrylic resin (2) to introduce a carboxyl group, good alkaline developability can be obtained. Examples of polybasic acids include, but are not limited to, adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. Examples of polybasic acid anhydrides include 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, succinic anhydride, and octenylsuccinic anhydride. The polybasic acids or polybasic acid anhydrides (a-3) may be used alone or in combination of two or more.

[0069] <Proportion of structural units of (meth)acrylic resin (2)> The ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group preferably accounts for 20 to 90 mol %, more preferably 30 to 80 mol %, and even more preferably 40 to 80 mol % of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (2). When the ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group is 20 mol % or more, curability is good. When the ethylenically unsaturated group-containing compound (m-2) having an epoxy group or an oxetanyl group is 80 mol % or less, solvent resistance and storage stability are good.

[0070] The other monomer (m-4) is preferably 10 to 80 mol%, more preferably 20 to 70 mol%, and even more preferably 20 to 60 mol% of the total monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (2). When the other monomer (m-4) is 10 mol% or more, storage stability is good. When the other monomer (m-4) is 80 mol% or less, sufficient alkali developability and adhesion are obtained.

[0071] The amount of the ethylenically unsaturated group-containing compound (a-2) having a carboxy group is preferably 20 to 100 moles, more preferably 60 to 100 moles, and even more preferably 90 to 100 moles, per 100 moles of the total of functional groups reactive with carboxy groups possessed by the monomers used in the radical polymerization when synthesizing the (meth)acrylic resin (2). When the amount of the ethylenically unsaturated group-containing compound (a-2) having a carboxy group is 20 moles or more, good curability is achieved.

[0072] The amount of the polybasic acid or polybasic acid anhydride (a-3) added when synthesizing the (meth)acrylic resin (2), i.e., relative to a total of 100 moles of hydroxy groups generated by ring-opening of the epoxy groups or oxetanyl groups derived from the compound (m-2), is preferably 10 to 90 moles, more preferably 30 to 80 moles, and even more preferably 40 to 70 moles, of the polybasic acid or polybasic acid anhydride (a-3). When the amount of the polybasic acid or polybasic acid anhydride (a-3) is 10 moles or more, alkaline developability is good. When the amount of the polybasic acid or polybasic acid anhydride (a-3) is 90 moles or less, fine line adhesion and storage stability are good. When the polybasic acid or polybasic acid anhydride (a-2) is trifunctional, i.e., when it is a polybasic acid or polybasic acid anhydride having three carboxy groups, the upper limit of the number of moles of the polybasic acid or polybasic acid anhydride (a-2) may be 40 moles or 30 moles.

[0073] [(B) Reactive diluent] The reactive diluent (B) is not particularly limited as long as it contains an ethylenically unsaturated double bond such as a vinyl group or a (meth)acryloyloxy group and is a low-molecular-weight compound other than the modified polyol compound (E). In this specification, a low-molecular-weight compound is a compound with a molecular weight of less than 1,000. Specific examples of the (B) reactive diluent include aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene; aromatic allyl compounds such as diallyl phthalate and diallylbenzene phosphonate; vinyl carboxylates such as vinyl acetate and vinyl adipate; (meth)acrylic monomers such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; and triallyl cyanurate. As the (B) reactive diluent, from the viewpoint of curability and solvent resistance, a compound having a plurality of (meth)acryloyloxy groups is preferred, and a compound having three or more (meth)acryloyloxy groups such as trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, etc. is more preferred. The (B) reactive diluents may be used alone or in combination of two or more.

[0074] [(C) Photopolymerization initiator] The (C) photopolymerization initiator is preferably a photoradical generator, and specific examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; acetophenone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; Examples of suitable photopolymerization initiators include ketal compounds such as phenone dimethyl ketal and benzil dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,-1-(O-acetyloxime); acylphosphine oxide photopolymerization initiators; and xanthone photopolymerization initiators. (C) Photopolymerization initiators may be used alone or in combination of two or more.

[0075] [(D) Solvent] The (D) solvent is not particularly limited as long as it does not react with the other components and can dissolve or disperse them. Specific examples of the (D) solvent include (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol ethyl ether acetate; esters such as ethyl acetate, butyl acetate, and isopropyl acetate; (poly)alkylene glycol alkyl ethers such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether, and diethylene glycol monomethyl ether; and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Among these, (poly)alkylene glycol monoalkyl ether acetates and (poly)alkylene glycol alkyl ethers are preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are more preferred. The (D) solvent may be used alone or in combination of two or more kinds.

[0076] The solvent used in the synthesis of (A) the alkali-soluble resin and the synthesis of (E) the modified polyol compound may be used as is without removing it, or a new solvent may be added.

[0077] [(E) Modified polyol compound] The modified polyol compounds described above can be used as the (E) modified polyol compound. When the photosensitive resin composition contains an (E) modified polyol compound having an ethylenically unsaturated group, good developability can be achieved, allowing the formation of a desired pattern shape. In addition, when the (E) modified polyol compound has multiple ethylenically unsaturated groups, the cured product of the photosensitive resin composition containing the (E) modified polyol compound has a crosslinked structure formed by photopolymerization of the ethylenically unsaturated groups of the (E) modified polyol compound, resulting in excellent solvent resistance. When the (E) modified polyol compound has multiple hydroxy groups, the cured product exhibits good adhesion to the adherend. When the (E) modified polyol compound has phenolic hydroxyl groups, the polymerization-inhibiting effect of the phenolic hydroxyl groups allows the amount of a typical low-molecular-weight polymerization inhibitor to be reduced, thereby suppressing the effects of a typical low-molecular-weight polymerization inhibitor, such as reduced adhesion.

[0078] [Polymerization inhibitor] As long as the effects of the present invention are not impaired, known polymerization inhibitors not having an ethylenically unsaturated group, such as MEHQ (4-methoxyphenol), BHT (dibutylhydroxytoluene), and methylhydroquinone, may be used in combination. However, these polymerization inhibitors remain free in the cured resin film even after photocuring of the photosensitive resin composition and act to impair adhesion to the substrate. Therefore, it is preferable to reduce the content of these polymerization inhibitors, and more preferably not use them at all. The photosensitive resin composition contains, for example, 0.01 to 0.3 mass% of a polymerization inhibitor not having an ethylenically unsaturated group. In one embodiment, the photosensitive resin composition does not contain a polymerization inhibitor not having an ethylenically unsaturated group. The upper limit of the content of the polymerization inhibitor not having an ethylenically unsaturated group in the photosensitive resin composition is, for example, 0.3 mass% or 0.2 mass%.

[0079] [Other ingredients] In addition to the components described above, the photosensitive resin composition of the first embodiment may contain known additives such as a photoacid generator, a photobase generator, a coupling agent, a leveling agent, a colorant (F) described later, a filler, etc. in order to impart predetermined properties. The amounts of these components to be added are not particularly limited as long as they are within a range that does not impair the effects of the present invention.

[0080] [Composition ratio of each ingredient] The amount of the (A) component is preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the total of the (A) alkali-soluble resin (also referred to as the (A) component), the (B) reactive diluent (also referred to as the (B) component), the (C) photopolymerization initiator (also referred to as the (C) component), and the (E) modified polyol compound (also referred to as the (E) component). When the (A) component is 10 parts by mass or more, good curability is obtained. When the (A) component is 70 parts by mass or less, good storage stability is obtained.

[0081] The amount of component (B) is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 15 to 30 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (E). When component (B) is 5 parts by mass or more, good curability is obtained. When component (B) is 50 parts by mass or less, good storage stability is obtained.

[0082] The amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (E). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0083] The amount of the solvent (D) is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, relative to 100 parts by mass of the total of the components (A), (B), (C), and (E).Within this range, the photosensitive resin composition is easy to handle.

[0084] The amount of component (E) is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, and even more preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), and (E). When component (E) is 0.05 part by mass or more, a good pattern shape and adhesion can be obtained. When component (E) is 50 parts by mass or less, good adhesion can be obtained.

[0085] <Photosensitive coloring composition> The photosensitive coloring composition according to one embodiment of the present invention contains a photosensitive resin composition and a colorant (F).

[0086] [(F) Colorant] The (F) colorant (also referred to as (F) component) is one that is soluble or dispersible in a solvent, and examples thereof include dyes and pigments. The (F) colorant may be a dye alone, a pigment alone, or a combination of a dye and a pigment, depending on the color of the pixel to be produced using the photosensitive coloring composition. When the photosensitive coloring composition is used as a material for a color filter, it is preferable to use a dye as the (F) colorant for the following reasons. Pigments are particles, while dyes are molecules. For this reason, when a dye is used as a colorant, light scattering in the color filter is suppressed compared to when a pigment is used, and the brightness of an image display device equipped with the color filter is increased.

[0087] As the dye, from the viewpoint of solubility in solvents and alkaline developers, interaction with other components in the photosensitive coloring composition, heat resistance of the photosensitive coloring composition, etc., it is preferable to use an acid dye having an acidic group such as a carboxylic acid or sulfonic acid, a salt of an acid dye with a nitrogen compound, a sulfonamide adduct of an acid dye, etc. In particular, it is preferable to use an anthraquinone-based, azo-based, xanthene-based, or phthalocyanine-based dye as the dye. Among them, it is preferable to use one or both of an anthraquinone-based dye and a xanthene-based dye, since a photosensitive coloring composition can be obtained that can produce a resin cured film with high transmittance.

[0088] Specifically, the dyes are: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; and acid red. 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274, 289, Rhodamine B; acid violet 6B; 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3, VALIFAST (trademark) BLUE 1603, 1605, 1621, 2606, 2620, 2670, and derivatives thereof. The dyes can be used alone or in combination of two or more types depending on, for example, the color of the desired pixel.

[0089] Pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 154, 166, 168, and 173. Examples of suitable pigments include red pigments such as 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as CI Pigment Green 7, 36, 58, 59, and 62; brown pigments such as CI Pigment Brown 23 and 25; and black pigments such as CI Pigment Black 1, 7, carbon black, titanium black, and iron oxide. Pigments can be used alone or in combination depending on the desired pixel color, for example.

[0090] When a pigment is used as the (F) colorant, a known dispersant may be contained in the photosensitive coloring composition to improve the dispersibility of the pigment. It is preferable to use a polymer dispersant that has excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. Commercially available polymer dispersants, such as EFKA (manufactured by EFKA CHEMICALS BV), Disperbyk (manufactured by BYK), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Lubrizol Corporation), may also be used.

[0091] [Composition ratio of each ingredient] The amount of component (A) is preferably 10 to 80 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 20 to 60 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (A) is 10 parts by mass or more, good curability is obtained. When component (A) is 80 parts by mass or less, good storage stability is obtained.

[0092] The amount of component (B) is preferably 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, and even more preferably 8 to 25 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (B) is 3 parts by mass or more, good curability is obtained. When component (B) is 40 parts by mass or less, good storage stability is obtained.

[0093] The amount of component (C) is preferably 0.1 to 10 parts by mass, more preferably 1 to 7 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (C) is 0.1 part by mass or more, good curability is obtained. When component (C) is 10 parts by mass or less, good adhesion is obtained.

[0094] The amount of component (E) is preferably 0.05 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, and even more preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (E) is 0.05 part by mass or more, a good pattern shape and adhesion can be obtained. When component (E) is 50 parts by mass or less, good adhesion can be obtained.

[0095] The amount of component (F) is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, relative to 100 parts by mass of the total of components (A), (B), (C), (E), and (F). When component (F) is 5 parts by mass or more, the desired degree of coloring can be obtained. When component (F) is 40 parts by mass or less, storage stability is good.

[0096] <(A) Method for producing alkali-soluble resin> The alkali-soluble resin (A) can be produced, for example, by the following production method. That is, a monomer, a polymerization solvent, and a radical polymerization initiator are mixed and radically polymerized in a nitrogen atmosphere, typically at 70°C to 130°C, to obtain a copolymer. When introducing functional groups such as ethylenically unsaturated groups and carboxy groups into the obtained copolymer, a catalyst is added as needed in a dry air atmosphere, and an addition reaction is carried out typically at 70°C to 130°C, to obtain the alkali-soluble resin (A).

[0097] The addition reaction may be carried out in the presence of a modified polyol compound (E). This reduces unintended crosslinking of ethylenically unsaturated groups and prevents the molecular weight of the alkali-soluble resin (A) from increasing excessively. In addition, the amount of polymerization inhibitors other than the modified polyol compound (E) can be reduced, thereby reducing the effects on the developability of the photosensitive resin composition and the photosensitive coloring composition, the adhesion of the cured product, and the like.

[0098] <Polymerization solvent> The polymerization solvent is not particularly limited as long as it is a solvent inert to the copolymerization reaction of the raw material monomers. As the polymerization solvent, those exemplified as the (D) solvent can be used. From the viewpoint of handling, it is preferable to use a (poly)alkylene glycol monoalkyl ether acetate as the polymerization solvent, and it is particularly preferable to use propylene glycol monomethyl ether acetate.

[0099] The amount of the polymerization solvent used is not particularly limited, but is preferably 30 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of the raw material monomers. When the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomers can be carried out stably, and coloration and gelation of the copolymer can be prevented. When the amount of the polymerization solvent used is 1,000 parts by mass or less, a decrease in the molecular weight of the copolymer due to chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0100] <Radical Polymerization Initiator> The radical polymerization initiator that can be used in the copolymerization reaction of the raw material monomers is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyrate) dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. The radical polymerization initiators may be used alone or in combination of two or more.

[0101] The amount of radical polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 16 parts by mass, relative to 100 parts by mass of the raw material monomer.

[0102] <Method for producing photosensitive resin composition> The photosensitive resin composition can be produced by mixing the above-mentioned components using a known mixing device. For example, it can be produced by sequentially mixing (A) an alkali-soluble resin, (B) a reactive diluent, (C) a photopolymerization initiator, and (D) a solvent. If necessary, a colorant (F) may be added. The (E) modified polyol compound may be mixed before the addition reaction for introducing functional groups such as ethylenically unsaturated groups and carboxyl groups when producing the (A) alkali-soluble resin, or may be added when mixing the (A) to (D) components. From the viewpoints of reducing unintended crosslinking of ethylenically unsaturated groups during the synthesis of the (A) alkali-soluble resin and preventing excessive increases in the molecular weight of the (A) alkali-soluble resin, it is preferable to mix the (E) modified polyol compound before the addition reaction when producing the (A) alkali-soluble resin.

[0103] The photosensitive resin composition thus obtained has excellent storage stability and can exhibit various excellent resist properties such as excellent solvent resistance, pattern adhesion, and developability, and can form a pattern with excellent reliability.By using a photosensitive coloring composition in which a colorant (F) is blended with a photosensitive resin composition, a color filter with excellent reliability can be provided.

[0104] <Cured resin film> A cured resin film can be obtained by irradiating a photosensitive resin composition with active energy rays to cure it. Specifically, the cured resin film can be produced by the following method. A photosensitive resin composition or a photosensitive coloring composition is applied to a substrate such as glass so that the average thickness of the final cured coating film is a predetermined value depending on the purpose, and then the coating film is heated, for example, at 50 to 150°C for 1 to 50 minutes to volatilize the solvent. Next, the entire surface of the coating film is exposed to light (for example, using a lamp USH-250BY manufactured by Ushio Inc., with an exposure dose of 40 mJ / cm). 2 ) and then baking, for example, at 50 to 200°C for 10 to 180 minutes to obtain a cured coating film. After volatilizing the solvent, the coating film is exposed to light through a photomask and developed with an alkaline developer to obtain a cured coating film having a predetermined pattern.

[0105] <Color filter> A color filter according to one embodiment has a cured product of a photosensitive coloring composition. The color filter has a color pattern formed using the photosensitive coloring composition. A color filter typically comprises a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries between the pixels, and a protective film formed on the pixels and the black matrix. In this configuration, known substrates and protective films can be used.

[0106] A color filter can be manufactured, for example, by the following method. First, a colored pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed wiring boards, array substrates, etc. can be used as appropriate.

[0107] The colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied to a substrate to form a coating film, and then the coating film is exposed to light through a photomask with a predetermined pattern to photocure the exposed portions. The unexposed portions are then developed with an alkaline aqueous solution and baked to form the desired colored pattern.

[0108] The method for applying the photosensitive coloring composition is not particularly limited, and can be screen printing, roll coating, curtain coating, spray coating, spin coating, or the like. After applying the photosensitive coloring composition, the solvent (D) may be evaporated by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary. The heating conditions are not particularly limited and may be appropriately set depending on the type of photosensitive coloring composition used. Generally, heating at a temperature of 50°C to 120°C for 30 seconds to 30 minutes is sufficient.

[0109] Next, the formed coating film is partially exposed by irradiating it with active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The amount of energy radiation to be irradiated may be appropriately selected depending on the composition of the photosensitive coloring composition, and may be, for example, 30 to 2000 mJ / cm. 2 The light source used for exposure is not particularly limited, but may be a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like.

[0110] The alkaline aqueous solution used for development is not particularly limited, but may include aqueous solutions of inorganic alkaline compounds such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amines such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; aqueous solutions of aniline compounds and their salts such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, and 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates; and aqueous solutions of p-phenylenediamine compounds and their salts. Additives such as antifoaming agents and surfactants may also be added to these aqueous solutions as needed. After development with the alkaline aqueous solution, the cured coating film is preferably washed with water and dried.

[0111] The baking conditions are not particularly limited, and the heat treatment may be carried out depending on the type of photosensitive coloring composition used. Generally, the heating may be carried out at 80 to 250° C. for 10 to 60 minutes.

[0112] The above-described coating, exposure, development, and baking processes can be repeated in sequence using the photosensitive coloring composition for the black matrix and the photosensitive coloring compositions for the red, green, and blue pixels to form a desired color pattern. Thereafter, a protective film is formed on the color pattern (each pixel of RGB and the black matrix). The protective film is not particularly limited, and any known film may be used.

[0113] The color filter produced in this manner is expected to have excellent solvent resistance and adhesion, and to suppress the bleeding out of low molecular weight components such as polymerization inhibitors.

[0114] <Image display element> An image display element according to one embodiment is an image display element equipped with a color filter, and specific examples thereof include liquid crystal display elements, organic EL display elements, and solid-state imaging elements such as CCD elements and CMOS elements. The image display element may be manufactured according to a conventional method. For example, when manufacturing a liquid crystal display element, a color filter is formed on a substrate, and then electrodes, spacers, and the like are formed in sequence. Then, electrodes, etc. are formed on another substrate, and the two are bonded together, after which a predetermined amount of liquid crystal is injected and sealed. [Example]

[0115] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0116] The raw materials used in the synthesis of the (E) modified polyol compound are shown below. Tannic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) Catechin (Fujifilm Wako Pure Chemical Industries, Ltd.) Myricetin (Fujifilm Wako Pure Chemical Industries, Ltd.) Glycidyl methacrylate (GMA, manufactured by NOF Corporation) 1,2,3,6-Tetrahydrophthalic anhydride (THPA, manufactured by New Japan Chemical Co., Ltd.)

[0117] A synthesis example of the (E) modified polyol compound is shown below.

[0118] [Synthesis Example 1] (Example 1) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 64.16 g of propylene glycol monomethyl ether acetate and 68.4 g of tannic acid, and the mixture was stirred while purging with nitrogen and heated to 80°C. Next, a mixture of 28.2 g of 2-isocyanatoethyl acrylate (KARENZ (registered trademark) AOI, manufactured by Showa Denko K.K.) and 0.15 g of tri(p-tolyl)phosphine (p-TPP) was added dropwise. After the dropwise addition, the mixture was allowed to react at 80°C for 5 hours to obtain the (E) modified polyol compound of Example 1.

[0119] [Synthesis Examples 2 to 4] (Examples 2 to 4) (E) Modified polyol compounds of Examples 2 to 4 were obtained in the same manner as in Example 1, except that the raw materials and the temperature of the modification reaction with 2-isocyanatoethyl acrylate or glycidyl methacrylate were changed as shown in Table 1.

[0120] [Synthesis Example 5] (Example 5) The (E) modified polyol compound of Example 5 was obtained in the same manner as in Example 1, except that 30.4 g of 1,2,3,6-tetrahydrophthalic anhydride (THPA) was added to the reaction solution after the modification reaction with 2-isocyanatoethyl acrylate and the mixture was reacted at 110°C for 1 hour.

[0121] [Synthesis Example 6] (Example 6) The (E) modified polyol compound of Example 6 was obtained in the same manner as in Example 2, except that 30.4 g of 1,2,3,6-tetrahydrophthalic anhydride (THPA) was added to the reaction solution after the modification reaction with glycidyl methacrylate and the mixture was reacted at 110°C for 1 hour.

[0122] [Table 1]

[0123] An example of synthesis of the alkali-soluble resin (A) is shown below.

[0124] [Synthesis Example 7] (copolymerization reaction) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 109.8 g of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen and heated to 120°C. Next, a mixture of 85.2 g (0.6 mol) of glycidyl methacrylate, 66.0 g (0.3 mol) of tricyclodecanyl methacrylate (TCDMA, manufactured by Showa Denko Materials Co., Ltd.), and 10.4 g (0.1 mol) of styrene (St, manufactured by Idemitsu Kosan Co., Ltd.), plus 18.0 g of t-butylperoxy-2-ethylhexanoate (TBO, polymerization initiator, manufactured by NOF Corporation, Perbutyl® O), was added dropwise from the dropping funnel to the flask over 2 hours. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to carry out the copolymerization reaction, yielding an addition copolymer solution ((A) alkali-soluble resin precursor). (Addition reaction 1) To the obtained solution, 41.9 g of acrylic acid (AA, manufactured by Kuraray Co., Ltd.), 0.6 g of dibutylhydroxytoluene (BHT, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a polymerization inhibitor (0.3 parts by mass relative to 100 parts by mass of the total of acrylic acid and resin solid content), and 0.6 g of tri(o-tolyl)phosphine (o-TPP, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a catalyst (0.3 parts by mass relative to 100 parts by mass of the total of acrylic acid and resin solid content), were added, and the mixture was heated at 110°C for 10 hours while blowing air into it. (Addition reaction 2) After confirming that the acid value was 1.0 mgKOH / g or less, 54.7 g (0.36 mol) of 1,2,3,6-tetrahydrophthalic anhydride (THPA, manufactured by New Japan Chemical Co., Ltd.) was added and reacted at 110°C for 2 hours, and 180 g of propylene glycol monomethyl ether acetate was added to obtain (A) an alkali-soluble resin solution (solid acid value 76 mgKOH / g, weight-average molecular weight 7000, ethylenically unsaturated group equivalent 474 g / mol).

[0125] [Synthesis Example 8] (copolymerization reaction) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 157.58 g of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen and heated to 120°C. Next, a mixture of 33.5 g (0.39 mol) of methacrylic acid (MAA, manufactured by Kuraray Co., Ltd.), 59.4 g (0.27 mol) of tricyclodecanyl methacrylate, and 59.8 g (0.34 mol) of benzyl methacrylate (BZMA, manufactured by Kyoeisha Chemical Co., Ltd.), plus 5.0 g of t-butylperoxy-2-ethylhexanoate (polymerization initiator, manufactured by NOF Corporation, Perbutyl® O), was added dropwise from the dropping funnel to the flask over 2 hours. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to carry out a copolymerization reaction, producing an addition copolymer (a precursor to the alkali-soluble resin (A)). (Addition reaction 1) The resulting reaction mixture was charged with 14.2 g (0.1 mol) of glycidyl methacrylate (NOF Corporation), 0.5 g of butylhydroxytoluene as a polymerization inhibitor (0.3 parts by mass per 100 parts by mass of acrylic acid and resin solids), and 0.5 g of tri(o-tolyl)phosphine as a catalyst (0.3 parts by mass per 100 parts by mass of acrylic acid and resin solids), and heated at 110 ° C for 10 hours while blowing air. After that, the reaction was terminated by confirming that the acid value was 40.0 mg KOH / g or less, and (A) alkali-soluble resin solution (solid acid value 103.2 mg KOH / g, weight average molecular weight 13700, ethylenically unsaturated group equivalent 1714 g / mol) was obtained.

[0126] [Synthesis Example 9] An alkali-soluble resin solution (A) (solid acid value 76.2 mg KOH / g, weight average molecular weight 7000, ethylenically unsaturated group equivalent 474 g / mol) was obtained in the same manner as in Synthesis Example 7, except that the modified polyol compound of Synthesis Example 1 was used instead of butylhydroxytoluene.

[0127] [Synthesis Example 10] An alkali-soluble resin solution (A) (solid acid value 103 mg KOH / g, weight average molecular weight 13,600, ethylenically unsaturated group equivalent 1,714 g / mol) was obtained in the same manner as in Synthesis Example 8, except that the modified polyol compound of Synthesis Example 1 was used instead of butylhydroxytoluene.

[0128] [Table 2]

[0129] [Example 7] (A) 150 parts by mass of the alkali-soluble resin obtained in Synthesis Example 7 as solids, (B) 50 parts by mass of dipentaerythritol hexaacrylate (DPHA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a reactive diluent, (C) 5 parts by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-, -1-(O-acetyloxime) (OXE-02, manufactured by BASF) as a photopolymerization initiator, (E) 25 parts by mass of the compound obtained in Synthesis Example 1 as a modified polyol compound, and (F) 50 parts by mass of VALIFAST (trademark) BLUE 2620 as a colorant were mixed, and propylene glycol monomethyl ether acetate was added as a solvent so that the total solids content was 30% by mass, and mixed to prepare a photosensitive coloring composition.

[0130] [Examples 8 to 17, Comparative Examples 1 to 7] A photosensitive coloring composition was obtained in the same manner as in Example 7, except that the raw materials and their blending amounts were as shown in Table 3 or 4. In Tables 3 and 4, PQMA means 4-hydroxyphenyl methacrylate (manufactured by Showa Denko K.K.).

[0131] <Fine line adhesion and development time> Each of the photosensitive coloring compositions of Examples 7 to 17 and Comparative Examples 1 to 7 was spin-coated onto a 10 cm x 10 cm glass substrate so that the coating film had a thickness of 2.5 μm. Thereafter, the glass substrate was heated at 90°C for 3 minutes to volatilize the solvent. Next, a pattern mask was placed on the coating film, and exposure (exposure dose 80 mJ / cm) was performed from above the mask using a Multilight ML-251D / B manufactured by Ushio Inc. and an irradiation optical unit PM25C-100. 2 ) and photocured. Thereafter, the coating was developed for 120 seconds with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, and the size of the smallest remaining pattern was determined as the fine line adhesion. During development, the time until the pattern no longer changed (development time) was confirmed using a microscope. In Comparative Examples 4 to 7, no coating film remained after development.

[0132] <Solvent resistance> Each of the photosensitive coloring compositions of Examples 7 to 17 and Comparative Examples 1 to 7 was spin-coated onto a 5 cm square glass substrate (alkali-free glass substrate) to a thickness of 2.5 μm after baking, and then heated at 90°C for 3 minutes to volatilize the solvent. The coating was then exposed to light with a wavelength of 365 nm to photocure the exposed areas, and then left in a dryer at a baking temperature of 100°C for 20 minutes to produce a cured coating. 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL glass bottle with a lid and placed at 80°C. The glass substrate with the cured coating was immersed in the solution and then left at 80°C for 5 minutes. The color change (ΔE*ab) of the test piece before and after immersion in propylene glycol monomethyl ether acetate was measured using a UV-1650PC spectrophotometer (Shimadzu Corporation). The ΔE*ab measurement results are shown in Tables 3 and 4. If ΔE*ab is 12.5 or less, it can be said that the solvent resistance is excellent. Note that Comparative Examples 4 to 7 were not evaluated.

[0133] <Pattern shape> For each of the photosensitive coloring compositions of Examples 7 to 17 and Comparative Examples 1 to 7, a coating film having a thickness of 2.5 μm was prepared in the same manner as in the evaluation of fine line adhesion and development time. A mask having a line and space pattern with a line width of 20 μm was placed on the coating film, and the film was exposed (exposure amount 50 mJ / cm ) using a Multilight ML-251D / B manufactured by Ushio Inc. and an irradiation optical unit PM25C-100. 2 ) and photocured. After irradiation, the coating was developed with a 0.2% by mass aqueous solution of potassium hydroxide for 120 seconds and then post-baked at 230°C for 30 minutes to obtain the desired pattern. The obtained pattern was observed with a scanning electron microscope (SEM) and evaluated as excellent if there was no undercut, good if there was slight undercut, and poor if there was undercut. In Comparative Examples 4 to 7, no coating film remained after development.

[0134] [Table 3]

[0135] [Table 4] [Industrial Applicability]

[0136] According to the present invention, a photosensitive resin composition is provided that gives a cured resin film with good adhesion and has excellent storage stability. Also provided are a cured resin film with excellent adhesion, a color filter having a cured product of a photosensitive coloring composition with excellent adhesion, and an image display device including the same. The photosensitive resin composition can be preferably used as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, and a resist for a color filter.

Claims

1. A part of the hydroxy groups of the polyol compound is modified to a structure having an ethylenically unsaturated group, The modified polyol compound has two or more aromatic rings, and at least one of the aromatic rings has one or more structures selected from a catechol structure and a pyrogallol structure.

2. The modified polyol compound according to claim 1, wherein the polyol compound is one or more selected from the group consisting of luteolin, taxifolin, myricetin, quercetin, rutin, catechin, epigallocatechin gallate, butein, piceatannol, and tannic acid.

3. The modified polyol compound according to claim 1, wherein the structure having an ethylenically unsaturated group is a structure having at least one selected from the group consisting of a (meth)acryloyloxy group and a vinyloxy group.

4. The modified polyol compound according to claim 1, wherein a polybasic acid or an anhydride thereof is further added to a portion of the hydroxy groups of the polyol compound.

5. The modified polyol compound according to claim 1, having a hydroxyl value of 30 to 900 mgKOH / g.

6. The modified polyol compound according to claim 1, wherein the ethylenically unsaturated group equivalent weight is 50 to 900 g / mol.

7. The modified polyol compound according to claim 4, wherein the modification rate of the hydroxy groups of the polyol compound is 5 to 90%.

8. (A) an alkali-soluble resin; (B) a reactive diluent; and (C) a photopolymerization initiator; (D) a solvent; (E) the modified polyol compound according to any one of claims 1 to 7; A photosensitive resin composition comprising:

9. With respect to 100 parts by mass of the total of (A), (B), (C), and (E), The alkali-soluble resin (A) is contained in an amount of 10 parts by mass to 70 parts by mass, The (B) reactive diluent is contained in an amount of 5 to 50 parts by mass, The composition contains 0.1 to 10 parts by mass of the (C) photopolymerization initiator, The solvent (D) is contained in an amount of 30 parts by mass to 1000 parts by mass, The modified polyol compound (E) is contained in an amount of 0.05 parts by mass to 50 parts by mass. The photosensitive resin composition according to claim 8.

10. A cured resin film comprising a cured product of the photosensitive resin composition according to claim 8.

11. A photosensitive coloring composition comprising the photosensitive resin composition according to claim 8 and (F) a colorant.

12. A cured resin film comprising a cured product of the photosensitive coloring composition according to claim 11.

13. A color filter having a colored pattern formed from a cured product of the photosensitive coloring composition according to claim 11.

14. An image display device comprising the color filter according to claim 13.

Images