JP2008248143A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition which exhibits a good alkali developability and is excellent in heat resistance and transparency. <P>SOLUTION: This curable resin composition having a specific structure can be formed into coating films extremely excellent in heat resistance and transparency, can exhibit the good alkali developability, and can suitably be used in fields such as resist materials, various coatings or paints. According to the present invention, good quality color filters free from the defects of patterns and development residues can be provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel photosensitive resin composition and use thereof.

  Conventionally, as a photosensitive resin composition excellent in heat resistance, for example, a resin composition containing a polymer obtained by polymerizing a monomer component containing maleimide and a curing component (see, for example, Patent Documents 1 and 2) A resin composition containing a polymer obtained by polymerizing a compound having a specific structure, which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester, together with a curing component (for example, see Patent Document 3) has been proposed.

  However, in the former resin composition containing a polymer derived from maleimide, since the maleimide polymer contains a nitrogen atom, the polymer is colored yellow to tan, and the transparency of the cured film becomes insufficient. There was a problem. This transparency problem is particularly noticeable when the thickness of the cured film is thick, and further, it may be further colored when heat-treated. Moreover, in the latter resin composition containing the ether dimer of 2- (hydroxyalkyl) acrylic acid ester, depending on the development conditions, there is a problem that the cured portion is lost and the pattern shape is deteriorated, and the development residue remains and the surface becomes rough. It sometimes occurred.

Japanese Patent Laid-Open No. 04-130128 JP 10-31308 A JP 2004-300204 A

  Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of forming a coating film excellent in solubility in an organic solvent or an alkali developer in addition to heat resistance and transparency, and the cured product. .

  The inventor has intensively studied to solve the above problems. As a result, a resin composition containing a compound having a specific structure, which is an ether dimer of 2- (hydroxyalkyl) acrylic acid ester, and a polymer obtained by copolymerizing acrylic acid as an essential component, together with a curing component, all at once. The present invention has been completed by finding out that the problem can be solved.

  That is, the photosensitive resin composition according to the present invention is a photosensitive resin composition comprising a polymer monomer component (a1) and a compound (B) having a radical polymerizable double bond, wherein the polymer Component (a1) is represented by the following general formula (1),

(In formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
It is a polymer (A) formed by copolymerizing a monomer component essentially comprising acrylic acid and

  The photosensitive resin composition of the present invention has the following general formula (1)

(In formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
And a polymer (A) obtained by copolymerizing a monomer component having acrylic acid as an essential component (hereinafter also referred to as “ether dimer”) as an essential component. Thereby, the photosensitive resin composition of this invention can form the cured coating film which was excellent also in heat resistance and transparency, and excellent in alkali developability. This is presumably because the ether dimer undergoes a cyclization reaction during polymerization to form a tetrahydropyran ring structure in the structural unit derived from the ether dimer.

  Hereinafter, the polymer (A) will be described. In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R1 and R2 is not particularly limited. Linear or branched alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, Alicyclic groups such as t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl Alkyl group; an alkyl group substituted with an aryl group such as benzyl; and the like. Among these, the number of carbon atoms is preferably 8 or less, and further, primary or secondary carbon substituents that are not easily removed by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl, 2-ethylhexyl, etc. are heat resistant. Is preferable. R1 and R2 may be the same type of substituents or different substituents.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate and di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 ′-[oxybis (methylene)] bis -2-propenoate is preferred. These ether dimers may be only one kind or two or more kinds.

  The ratio of the ether dimer in the monomer component in obtaining the polymer (A) is not particularly limited, but is 2 to 60% by weight, preferably 5 to 50% by weight, more preferably all monomer components. 5 to 40% by weight, particularly preferably 5 to 30% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight polymer or may be easily gelled during polymerization, and the dissolution rate in a solvent or an alkaline developer will be slow. Since there is a tendency, it is not preferable. On the other hand, if the amount is too small, the film performance such as transparency and heat resistance may be insufficient.

  The proportion of acrylic acid is not particularly limited, but is 5 to 60% by weight, preferably 5 to 50% by weight, more preferably 7 to 40% by weight, and most preferably 7 to 25% by weight in the total monomer components. It is good. When the amount of the monomer having an acid group is less than 5% by weight, it becomes difficult to develop, and when the amount is more than 60% by weight, the sensitivity to development is too high, and the control becomes difficult, and the dissolution in an organic solvent becomes difficult. May be reduced.

  The polymer (A) may have another acid group in addition to acrylic acid. By having another kind of acid group in addition to acrylic acid, the resulting photosensitive resin composition can be a photosensitive resin composition having better alkali developability. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be used alone or in combination of two or more.

  In order to introduce another acid group in addition to acrylic acid into the polymer (A), for example, a monomer having an acid group and / or a monomer capable of imparting an acid group after polymerization (hereinafter referred to as “a single group for introducing an acid group”). May be referred to as a “mer”.) As a monomer component. In addition, when introducing an acid group using a monomer capable of imparting an acid group after polymerization as a monomer component, for example, a treatment for imparting an acid group as described later is required after the polymerization.

  Examples of the monomer having an acid group include monomers having a carboxyl group such as methacrylic acid, itaconic acid and 4-vinylbenzoic acid, monomers having a phenolic hydroxyl group such as p-hydroxystyrene and N-hydroxyphenylmaleimide, and anhydride. And monomers having a carboxylic anhydride group such as maleic acid and itaconic anhydride. Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate. These monomers for introducing an acid group may be only one type or two or more types. The acrylic acid in the monomer having an acid group is preferably 30% by weight or more, more preferably 50% by weight or more, particularly preferably 80% by weight or more, and most preferably only acrylic acid. When the ratio of acrylic acid in the monomer having an acid group is less than 30% by weight, the solubility in an organic solvent or an alkali developer, which is a feature of the present invention, is inferior, the pattern shape is deteriorated, and the pattern is missing. May occur.

  The polymer (A) is preferably a polymer having a radical polymerizable double bond. Thereby, the said polymer (A) serves as a part or all of the compound (B) which has the radically polymerizable double bond mentioned later.

  In order to introduce a radical polymerizable double bond into the polymer (A), for example, a monomer capable of providing a radical polymerizable double bond after polymerization (hereinafter referred to as “monomer for introducing a radical polymerizable double bond”). )) As a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radically polymerizable double bond after the polymerization include, for example, monomers having a carboxyl group such as acrylic acid, methacrylic acid, and itaconic acid; and carboxylic acid anhydride groups such as maleic anhydride and itaconic anhydride. Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

  When the monomer component for obtaining the polymer (A) also includes a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited. 5 to 70% by weight, preferably 10 to 60% by weight. In the present application, a polymer having both properties (A) and (B) is expressed formally as a composition.

  The monomer component for obtaining the polymer (A) is an essential component of the ether dimer, a monomer for introducing an acid group other than acrylic acid and acrylic acid, and a radical polymerizable property. In addition to the monomer for introducing a double bond and the monomer for introducing an epoxy group, a copolymer for improving properties such as adhesion to a substrate, developability, and film hardness, if necessary. It is desirable to add a polymerizable monomer.

  Examples of the copolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc. (Meth) acrylic acid esters; aromatic vinyl compounds such as styrene, vinyltoluene and α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadiene or substitution such as butadiene and isoprene Butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate; and the like. Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, styrene, and vinyltoluene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more.

  When the monomer component in obtaining the polymer (A) also includes the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, and 85% by weight or less. Is more preferably 80% by weight or less.

  The polymer (A) can be easily obtained by polymerizing at least the monomer component essentially comprising the ether dimer and acrylic acid. At this time, the cyclization reaction of the ether dimer proceeds simultaneously with the polymerization to form a tetrahydropyran ring structure.

  The method for the polymerization reaction of the monomer component is not particularly limited, and various conventionally known polymerization methods can be employed, but the solution polymerization method is particularly preferable. The polymerization temperature and the polymerization concentration (polymerization concentration (%) = [total weight of monomer component / (total weight of monomer component + solvent weight)] × 100) are determined based on the monomer component used. Although it varies depending on the type and ratio, and the molecular weight of the target polymer, the polymerization temperature is preferably 40 to 150 ° C. and the polymerization concentration is 5 to 50%, and more preferably, the polymerization temperature is 60 to 130 ° C. and the polymerization concentration is 10%. It should be ˜40%.

  When a solvent is used in the polymerization of the monomer component, a solvent used in a normal radical polymerization reaction may be used as the solvent. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide; Etc. These solvents may be used alone or in combination of two or more.

  When polymerizing the monomer component, a commonly used polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of initiator used may be appropriately set according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. From the standpoint that several thousand to several tens of thousands of polymers can be obtained, the content is 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on all monomer components.

  When polymerizing the monomer component, a chain transfer agent that is usually used may be added, if necessary, for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid and methyl mercaptoacetate, and α-methylstyrene dimer. Preferred are n-dodecyl mercaptan and mercaptoacetic acid, which can be reduced and easily obtained. When a chain transfer agent is used, the amount used may be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited, but without gelation In terms of being able to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, it is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight based on all monomer components. .

  In the polymerization reaction, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously, but the cyclization rate of the ether dimer does not necessarily need to be 100 mol%.

  When obtaining the polymer (A), in addition to acrylic acid as a monomer component, a monomer capable of imparting the above-mentioned acid group is used, and when an acid group is introduced thereby, a treatment for imparting an acid group after polymerization Need to do. The treatment for imparting an acid group varies depending on the type of monomer that can impart an acid group to be used. For example, when a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is used, for example, What is necessary is just to make it add acid anhydrides, such as a succinic anhydride, a tetrahydrophthalic anhydride, and a maleic anhydride, When using the monomer which has epoxy groups, such as glycidyl (meth) acrylate, Hydroxyl group formed after adding a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol, or after adding an acid such as (meth) acrylic acid For example, an acid anhydride such as succinic acid anhydride, tetrahydrophthalic acid anhydride, maleic acid anhydride may be added. , In the case of using a monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate may be, for example, so as to be added with a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid.

  When obtaining the polymer (A), the monomer capable of imparting the radical polymerizable double bond described above is used as the monomer component, and when the radical polymerizable double bond is introduced thereby, the radical polymerizable double bond is obtained after the polymerization. It is necessary to perform processing for imparting a double bond. The treatment for imparting the radical polymerizable double bond varies depending on the type of monomer that can impart the radical polymerizable double bond to be used. For example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) A compound having an epoxy group such as acrylate, o- (or m-, or p-) vinylbenzylglycidyl ether and a radically polymerizable double bond may be added, such as maleic anhydride or itaconic anhydride. When a monomer having a carboxylic acid anhydride group is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth) acrylate may be added. Glycidyl (meth) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (ma When a monomer having an epoxy group such as m- or p-) vinylbenzyl glycidyl ether is used, a compound having an acid group such as (meth) acrylic acid and a radical polymerizable double bond is added. You can do it.

  Although the said polymer (A) weight average molecular weight is not restrict | limited in particular, Preferably it is 2000-200000, More preferably, it is 5000-100000. When the weight average molecular weight exceeds 200,000, the viscosity becomes too high to form a coating film, and when it is less than 2000, sufficient heat resistance tends to be hardly exhibited.

  The polymer (A) has an acid value of preferably 30 to 500 mgKOH / g, more preferably 50 to 400 mgKOH / g. When the acid value of the polymer (A) is less than 30 mgKOH / g, it becomes difficult to apply to alkali development, and when it exceeds 500 mgKOH / g, the viscosity tends to be too high to form a coating film.

  The photosensitive resin composition of the present invention only needs to contain the polymer (A) as a polymer component (A). In addition to the polymer (A), for example, a (meth) acrylic resin, a styrene resin A conventionally known polymer such as a butadiene-based resin that is usually used in a photosensitive resin composition may be used. In addition, when including polymers other than the said polymer (A), it is preferable that content of the said polymer (A) in a polymer component (A) shall be 50 weight% or more.

  The photosensitive resin composition of the present invention comprises a compound (B) having a radical polymerizable double bond as an essential component. Thereby, the photosensitive resin composition of this invention will express favorable sclerosis | hardenability.

  The compound (B) having a radical polymerizable double bond includes an oligomer and a monomer. Examples of the oligomer include unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, and acrylic having a double bond in the side chain. Examples of the monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyl toluene, divinylbenzene, diallyl phthalate, diallylbenzene phosphonate; vinyl acetate, adipine Vinyl ester monomers such as vinyl acid; (meth) acrylates such as methyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate, (2-oxo-1,3-dioxolan-4-yl) -methyl (meth) acrylate mono (Di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Polyfunctional (meth) acrylates such as pentaerythritol hexa (meth) acrylate and tris (hydroxyethyl) isocyanurate tri (meth) acrylate Over preparative; triallyl cyanurate; epoxy resin (meth) epoxy such as by adding acrylic acid (meth) acrylate; and the like. Of these, polyfunctional (meth) acrylates are preferable, and dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate are preferable in terms of sensitivity, mechanical strength after curing, industrial availability, and the like.

  The content ratio of the compound (B) having the radical polymerizable double bond in the photosensitive resin composition of the present invention is preferably 5 to 1000% by weight, more preferably 10 to 10% by weight with respect to the polymer component (A). 600% by weight.

  In the photosensitive resin composition of this invention, it is preferable that a photoradical generator is further included as a polymerization initiator (C). Specifically, when a photo radical generator is included as the polymerization initiator (C), the photosensitive resin composition of the present invention can be photocured by radical polymerization by irradiating light energy such as ultraviolet rays. It becomes. Even when the polymerization initiator (C) is not contained, the photosensitive resin composition of the present invention is based on radical polymerization by applying high energy radiation energy such as X-rays and electron beams, and thermal energy. Curing is possible.

  Examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenone such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone. Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpho Bruno - propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butanone-1; acylphosphine oxides and xanthones and the like.

  When the photosensitive resin composition of this invention contains the said photoradical generator, the content rate is preferably 0.1-50 weight with respect to the total amount of a polymer component (A) and a hardening component (B). %, More preferably 0.5 to 30% by weight.

  The photosensitive resin composition of this invention may contain the solvent as a diluent as needed.

  As the solvent, as long as the polymer component (A), the curing component (B), and the polymerization initiator (C) to be contained as needed are uniformly dissolved and do not react with each component, There is no particular limitation. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform and dimethyl sulfoxide; Etc. In addition, what is necessary is just to set content of a solvent suitably according to the optimal viscosity at the time of using a resin composition.

  In the present invention, dyes and pigments may be included as necessary. A pigment is desirable in terms of heat resistance and light resistance. As the pigment, red (Red), C.I. I. No. 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, etc. as green. I. Pig. 7, 36, C. blue as blue. I. No. 15, 22, 60, 64, etc., yellow as C.I. I. No. 20, 24, 83, 86, 93, 109, 110, 117, 139, 153, etc. I. No. 19, 23, 29, 30, 40, 50, etc. I. No. 7 or the like is generally used.

  In addition to the polymer component (A), the curing component, the polymerization initiator (C), the solvent, a pigment and a dye, the photosensitive resin composition of the present invention is within a range that does not impair the effect of the present invention. , Fillers such as aluminum hydroxide, talc, clay, barium sulfate, antifoaming agent, coupling agent, leveling agent, sensitizer, mold release agent, lubricant, plasticizer, antioxidant, UV absorber, flame retardant Further, it may contain known additives such as a polymerization inhibitor, a thickener, and a dispersant.

  In the photosensitive resin composition of the present invention, the polymer component (A) and the curing component (B) which are essential components (however, as described above, the polymer (A) can also serve as the curing component (B). In this case, the essential component is only the polymer component (A).) And the polymerization initiator (C), the solvent and other additives to be contained as necessary are prepared by uniformly mixing. be able to.

  The photosensitive resin composition of the present invention is excellent in transparency and heat resistance, and can be used for applications such as resist materials, various coating agents, paints, etc., and in particular, color filters and optical waveguides are produced. Therefore, it can be suitably used as an alkali developing negative resist material for the purpose. Furthermore, since the polymer (A) also has good pigment dispersibility due to the tetrahydropyran ring structure in its structure, it can be suitably used for a colored photosensitive resin composition for a color filter.

  The color filter of the present invention is a color filter in which a cured resin layer is provided on a substrate, wherein the resin composition to be the cured resin layer is the photosensitive resin composition of the present invention. The color filter is an optical filter having a fine pixel of at least three primary colors and a black matrix separating them on a transparent substrate, which is necessary for colorization of an image. The three primary colors are generally red (R). Green (G) and blue (B) are used. Specific examples of the member constituting the color filter include three primary color (RGB) pixels, a resin black matrix, a protective film, and a columnar spacer. The color filter of the present invention includes at least each member constituting the filter. One should just be formed by hardening the said photosensitive resin composition. In addition, when it contains a pigment, it is preferable to also contain a dispersing agent. As the dispersant, a known dispersant such as a surfactant, an acrylic block or graft copolymer having a nitrogen atom, or a pigment derivative can be used.

The curable resin composition of the present invention can form a coating film that is extremely excellent in heat resistance and transparency. For example, it can be suitably used in applications such as resist materials, various coating agents, and paints. Can do. Further, according to the present invention, it is possible to provide a color filter of good quality free from pattern defects and development residues. Furthermore, according to the present invention, it is possible to provide a display device with high display quality that has high luminance and color purity and does not cause color unevenness.

(Example 1)
A separable flask with a cooling tube was charged with 100 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), purged with nitrogen, and then heated to 90 ° C. On the other hand, in the dropping tank 1, 10.0 parts of dimethyl-2,2 ′-[oxybis (methylenebis)]-2-propionate, 40.1 parts of cyclohexyl methacrylate, 28.2 parts of methyl methacrylate, 20.7 parts of acrylic acid, 2.0 parts of t-butylperoxy-2-ethylhexanoate and 80 parts of PGMEA were mixed. In addition, 3.1 parts of β-mercaptopropionic acid and 6 parts of PGMEA were mixed in the dropping tank 2. While maintaining the reaction temperature at 90 ° C., dropwise addition was performed from the dropping tanks 1 and 2 to the reaction tank at a constant rate over 2.5 hours. After maintaining the temperature at 90 ° C. for 30 minutes, 0.5 part of t-butylperoxy-2-ethylhexanoate was added, and the reaction was further continued at 90 ° C. for 30 minutes. Thereafter, the reaction temperature was raised to 115 ° C., and the reaction was continued for 1.5 hours. Once cooled to room temperature, 24.7 parts of glycidyl methacrylate, 0.038 part of 6-t-butyl-2,4-xylenol and 0.38 part of dimethylbenzylamine were added to adjust the oxygen concentration to 7%. -The temperature was raised to 110 ° C while bubbling air mixed gas, and the reaction was performed for 6 hours. Thereafter, the temperature was raised to 115 ° C. and reacted for 2 hours to complete the reaction and cooled to room temperature to obtain a resin solution 1.

  The weight average molecular weight measured by GPC using polystyrene as a standard substance is 9000, the solid content concentration obtained by drying at 160 ° C. under vacuum is 40.1%, and the acid value per solid content determined by the titration method is It was 70 mgKOH / g.

  C. I. Pigment Green 36: 10 parts, 10 parts of resin solution 1 in terms of solid content, 10 parts of dipentaerythritol pentaacrylate, 3 parts of “Disperbik 161” manufactured by Big Chemie as a dispersant, Irgacure 907 manufactured by Ciba-Gigi Co., Ltd. as a photopolymerization initiator : After mixing 5 parts and diluting with PGMEA so that the total solid content excluding the solvent would be 10%, add 200 parts by weight of 0.5 mm zirconia beads to the solid content, and disperse with a paint shaker for 3 hours. Then, a colored photosensitive resin composition 1 was obtained.

The colored photosensitive resin composition 1 was spin-coated on a 10 cm × 10 cm non-alkali glass substrate and pre-baked at 100 ° C. for 3 minutes to prepare a coating film 1 having a thickness of 2 μm.
(Evaluation of solvent resolubility)
It was 10 seconds when the time until the coating film 1 melt | dissolved was measured while immersing the coating film 1 in PGMEA and stirring with a magnetic stirrer.
(Developability evaluation)
The coating film 1 was exposed with a high-pressure mercury lamp through a photomask at 100 mJ, and developed with a 0.04% aqueous potassium hydroxide solution. Furthermore, it was heated in a clean oven at 230 ° C. for 1 hour to complete the curing.

When the obtained pattern was observed with an optical microscope, the pattern shape was good, and no development residue was observed in the unexposed area. Moreover, although it wiped off with the clean white cloth, there was no color transfer.

(Comparative Example 1)
Resin solution 2 was obtained in the same manner as in Example 1 except that 24.7 parts of methacrylic acid and 24.2 parts of methyl methacrylate were used instead of acrylic acid. The weight average molecular weight was 9,500, the solid content was 40.3%, and the acid value per solid content was 70 mgKOH / g.

For the resin solution 2 obtained, the same operation as in Example 1 was performed to obtain a coating film 2.
The dissolution time of the coating film 2 in PGMEA was 15 seconds.

  When the obtained pattern was observed with an optical microscope, the linearity of the pattern was inferior, and some of the chips were observed. Further, a residue was observed in the unexposed area, and a slight white color transfer was observed when wiping with a clean white cloth was performed.

Claims (5)

A photosensitive resin composition comprising: (a1) as a monomer component and a polymer (A) having acrylic acid as essential components; and a compound (B) having a radical polymerizable double bond.
However, the polymer monomer component (a1) is represented by the following general formula (1)

(In formula (1), R1 and R2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
It is a compound shown by these. 2. The photosensitive resin composition, wherein the polymer (A) according to claim 1 further has a radical polymerizable double bond in a side chain. The photosensitive resin composition in any one of Claim 1 or 2 which also contains a photoradical generator as a polymerization initiator (C). In the color filter by which a cured resin layer is provided on a board | substrate, the resin composition used as the said cured resin layer is the photosensitive resin composition in any one of Claim 1 to 3 characterized by the above-mentioned. Color filter. In a display device using a color filter in which a cured resin layer is provided on a substrate, the resin composition to be the cured resin layer is the photosensitive resin composition according to any one of claims 1 to 4. A display device characterized by that.