TWI485184B - An alkali soluble silicone resin-containing alkali-soluble resin and a photosensitive resin composition, and a cured product using a photosensitive resin composition - Google Patents

Description

An alkali-soluble resin containing a polyoxyxylene resin and a photosensitive resin composition, and a cured product using a photosensitive resin composition

The present invention relates to a photosensitive resin which is cured by irradiation with ultraviolet rays or electron beams, and which is soluble in alkali, a photosensitive resin composition containing the pattern which can be formed by alkali image processing, and hardening using the photosensitive resin composition. Things.

Polyoxane resins are used in a wide range of fields such as electronic materials because of their excellent electrical properties, adhesion, heat resistance, and low water absorption. In particular, an epoxy polyoxyalkylene resin having an epoxy group in the molecule has better weather resistance and light resistance than an aromatic epoxy resin such as bisphenol A diglycidyl ether or phenol novolak epoxy resin. It is suitable as a blocking agent for light-emitting diodes (LEDs). More specifically, the light emitted from the LED element and the heat can be used to reduce resin change and discoloration over time. However, these resins have no pattern formation energy by alkali development treatment, and thus their use is limited.

Further, a resin composition suitable for use in an electronic material field such as an LED sealing agent, for example, disclosed in Patent Document 1, an epoxy resin obtained by hydrogenating an aromatic epoxy resin and a polyvalent carboxylic acid An alicyclic epoxy resin obtained by oxidizing an epoxy resin and a cyclic olefin with an equivalent weight of 230 to 1000 g/eq, and an epoxy resin composition for sealing using the same. Patent Document 2 discloses that a polyisocyanate compound having an epoxy group and a vinyl group and a polyoxyalkylene compound are added, and a polyoxyalkylene compound having an epoxy group-containing isocyanuric acid is branched and introduced. Patent Document 3 discloses a resin composition for a color filter protective film using an epoxy compound having a bisphenol fluorene skeleton. However, the exemplified compound does not have a pattern forming ability by alkali imaging treatment.

Further, Patent Document 4 discloses an alkali-soluble aromatic resin compound for a color filter having a polymerizable double bond and a carboxyl group. However, since the exemplified compound has an aromatic group, the resin may be deteriorated due to light and heat emitted from an LED or the like, and may be discolored over time.

Prior technical literature

Patent literature

[Patent Document 1] JP-A-2003-277473

[Patent Document 2] JP-A-2004-099751

[Patent Document 3] Special Opening No. 2004-69930

[Patent Document 4] License No. 3455296

In order to solve the problem of the prior resin composition, the present inventors have intensively reviewed and found that the dicarboxylic acid is obtained by reacting an epoxy polyoxyalkylene compound with a carboxylic acid having a polymerizable double bond. The alkali-soluble polyoxyalkylene resin which is suitable for forming a photosensitive resin composition can be obtained by reacting with its acid monoanhydride. In addition, the alkali-soluble polyoxyalkylene resin can be used to obtain a photosensitive resin composition that imparts alkali developability while maintaining the weather resistance, light resistance, and heat resistance of the polyoxyxene resin.

Therefore, an object of the present invention is to provide an alkali-soluble resin containing a polyoxyalkylene resin which is excellent in weather resistance, light resistance, heat resistance and the like and which can form a photosensitive resin composition of a fine pattern.

Further, another object of the present invention is to provide a photosensitive resin composition which can form a fine pattern having excellent weather resistance, light resistance, heat resistance and the like.

Further, another object of the present invention is to provide a cured product which is not deteriorated by light or heat, discolored over time, and the like.

In other words, the present invention is an alkali-soluble resin having a carboxylic acid residue and a polymerizable unsaturated group in one molecule, which is represented by the following general formula (1).

【化1】

(wherein R ₁ is a hydrocarbon group having 1 to 10 carbon atoms; R ₂ is a hydrocarbon group having 1 to 20 carbon atoms; the inside may contain an etheric oxygen atom; X is a divalent substituent which may contain a hetero atom internally; Y is a different The melamine ring skeleton bond contains a substituent of a polymerizable double bond and a carboxyl group; Z is a hydrogen atom, or a substituent of a hetero-cyanylene ring-bonding polymerizable double bond and a carboxyl group; m, n and p is independently from 0 to 100).

Furthermore, the present invention is an alkali-soluble resin represented by the following general formula (1') wherein n is 0 in the above general formula (1).

[Chemical 2]

(wherein R ₁ , R ₂ , X, Y, Z are the same as defined above; m and p are independently from 0 to 100).

Further, the present invention is characterized in that it contains an essential component (i) an alkali-soluble resin having a carboxylic acid residue and a polymerizable unsaturated group in one molecule, represented by the following general formula (1).

[化3]

(wherein R ₁ is a hydrocarbon group having 1 to 10 carbon atoms; R ₂ is a hydrocarbon group having 1 to 20 carbon atoms; the inside may contain an etheric oxygen atom; X is a divalent substituent which may contain a hetero atom internally; Y is a different a melamine ring skeleton bond containing a substituent of a polymerizable double bond and a carboxyl group; Z is a hydrogen atom, or a hetero-cyano ring skeleton bond containing a polymerizable double bond and a substituent of a carboxyl group; m, n And p is independent from 0 to 100).

(ii) a photopolymerizable monomer having at least one or more ethylenically unsaturated bonds, and (iii) a photosensitive resin composition of a photopolymerization initiator.

Preferred embodiments of the present invention are as follows. That is, in the general formula (1), X is a divalent substituent which may contain a hetero atom in the interior, and is preferably a divalent substituent represented by the following general formula (2), and Y is a heterocyanogenic ring skeleton bond. The substituent of the polymerizable double bond and the carboxyl group is preferably a substituent represented by the following general formula (3), and Z is a hydrogen atom, or a hetero-cyanyl ring skeleton is bonded with a polymerizable double bond and a carboxyl group. The substituent in the case where Z is not a hydrogen atom is preferably the above-mentioned alkali-soluble resin represented by the following general formula (3), and the photosensitive resin using the alkali-soluble resin as the component (i) for addition Composition.

【化4】

【化5】

(wherein R ₃ is a hydrogen atom or a methyl group; R ₄ is a hydrocarbon group having 1 to 20 carbon atoms, and may have an etheric oxygen atom or an ester bond; R ₅ is a hydrocarbon group having 1 to 20 carbon atoms; and an ether may be contained therein; The oxygen atom; L is a substituent represented by the following general formula (4)).

【化6】

(wherein M is a 2 or 3 valent carboxylic acid residue; q is 1 or 2).

In a preferred embodiment of the present invention, the alkali-soluble resin represented by the following general formula (1') and the photosensitive resin represented by the (i) component using the alkali-soluble resin are 0. Composition.

【化7】

(wherein, R ₁ , R ₂ , X, Y, and Z are the same as the general formula (1); m and p are independently from 0 to 100).

Further, the photosensitive resin composition of the present invention may be a photosensitive resin composition containing the following components in addition to the above components (i) to (iii).

(iv) an epoxy resin or epoxy compound having two or more epoxy groups

(However, (iv) is an epoxy resin derived from a phenol, an epoxy compound derived from an olefin compound having a ring structure, an epoxy compound having a heterocyanogenic ring skeleton, or a polyfunctional epoxy polyoxyalkylene oxide. Resin).

Moreover, the present invention is a cured product obtained by applying the photosensitive resin composition and then curing it.

The alkali-soluble resin represented by the general formula (1) of the present invention has higher weather resistance, light resistance, and heat resistance than the resin used in the resin composition used in the field of electronic materials, and has alkali developability. . That is, a cured product having excellent weather resistance, light resistance, and heat resistance can be obtained, and a fine pattern can be formed. Therefore, the alkali-soluble resin of the present invention is highly suitable as a protective layer, a sealing agent, and an adhesive for a semiconductor device such as a color filter-related material.

In addition, since the photosensitive resin composition of the present invention contains the alkali-soluble resin represented by the general formula (1), it has higher weather resistance, light resistance, and heat resistance than the resin composition previously used in the field of electronic materials. And has alkali imaging properties. That is, a cured product having excellent weather resistance, light resistance, and heat resistance can be obtained, and a fine pattern can be formed. Therefore, the photosensitive resin composition of the present invention is extremely suitable as a protective layer, a sealing agent, and an adhesive for a semiconductor device such as a color filter-related material.

Form of implementing the invention

The alkali-soluble resin and photosensitive resin composition of the present invention will be described in detail below.

The alkali-soluble resin represented by the general formula (1) has a radical polymerizable property as a photopolymerizable double bond derived from a polyvalent alcohol compound having a (meth)acrylic group, and contains an acid anhydride. It is acidic and has alkali solubility. In addition, the photosensitive resin composition of the present invention is a resin composition having a property of an alkali-developing photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1) as a main component.

The alkali-soluble resin of the general formula (1) is obtained by reacting an epoxy group of an epoxy polyoxyalkylene compound with (meth)acrylic acid, and then obtaining a polyvalent alcohol compound having a polymerizable double bond and then a dicarboxylic acid. Or a carboxyl group-containing polyoxyalkylene resin obtained by reacting the acid monoanhydride. Since the alkali-soluble resin of the general formula (1) retains a polymerizable double bond and a carboxyl group, it can impart excellent photocurability, good developability, and patterning properties to the alkali-developing photosensitive resin composition.

The method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail below. First, the alkali-soluble resin of the general formula (1) is a polymerized double obtained by reacting a polyfunctional epoxy polyoxyalkylene compound represented by the general formula (5) with a carboxylic acid having at least one polymerizable double bond. The polyvalent alcohol compound of the bond is derived.

【化8】

(wherein R ₁ is a hydrocarbon group having 1 to 10 carbon atoms; R ₂ is a hydrocarbon group having 1 to 20 carbon atoms; the inside may contain an etheric oxygen atom; and X is a divalent substituent which may contain a hetero atom internally; A is a different The melamine ring skeleton is bonded to a substituent having an epoxy group; G is a hydrogen atom, or a heterotrisinyl ring is bonded to a substituent having an epoxy group; m, n and p are independently 0 to 100)).

When the alkali-soluble resin of the present invention is produced, it is more preferred that the polyfunctional epoxy polyoxyalkylene compound represented by the general formula (6) is reacted with a carboxylic acid having at least one polymerizable double bond to form a polymerization double The polyvalent alcohol compound of the bond is derived.

【化9】

(wherein R ₁ is a hydrocarbon group having 1 to 10 carbon atoms; R ₂ is a hydrocarbon group having 1 to 20 carbon atoms; the inside may contain an etheric oxygen atom; X is a divalent substituent which may internally contain a hetero atom; and G is hydrogen The atom, or the iso-cyanide ring skeleton, has a substituent containing an epoxy group; m, n and p are independently from 0 to 100).

R ₁ is a hydrocarbon group having 1 to 10 carbon atoms. Such hydrocarbon groups are, for example, a linear hydrocarbon group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, an isooctyl group or a decyl group, or an aliphatic cyclic hydrocarbon group such as a cyclohexyl group. The aromatic hydrocarbon group such as a phenyl group, but not limited thereto, may be the same or different, and is preferably a methyl group. R ₂ is a hydrocarbon group having 1 to 20 carbon atoms and may have an etheric oxygen atom inside. Such hydrocarbon groups are, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a dodecyl group or a divalent substituent represented by the following general formula (7). Without being limited thereto, they may be the same or different, and preferably a propyl group.

【化10】

(wherein R ₆ is a hydrocarbon group having 1 to 17 carbon atoms or a single bond).

In the general formula (5), A is a substituent in which a heterocyanogenic ring skeleton is bonded to an epoxy group-containing group. Further suitable is represented by -R ₇ -R ₈ -(R ₉ -E) _l . Wherein R ₈ is a group formed by a heterocyanogenic ring skeleton, and R ₇ and R _{9 are} preferably a straight bond or a chain hydrocarbon group, and may contain a hetero atom. E is an epoxy group, and l is from 1 to 2, preferably 2.

In the general formula (5), G is a hydrogen atom, or a hetero-cyanyl ring skeleton is bonded to a substituent having an epoxy group. Further, a substituent other than a hydrogen atom is preferably represented by -R ₇ -R ₈ -(R ₉ -E) _l . Wherein R ₈ is a group formed by a heterocyanogenic ring skeleton, and R ₇ and R _{9 are} preferably a straight bond or a chain hydrocarbon group, and may contain a hetero atom. E is an epoxy group, and l is from 1 to 2, preferably 2. A preferred specific example is a substituent represented by the following general formula (8).

【化11】

In the general formula (5), X is a divalent substituent which may contain a hetero atom internally. These substituents are, for example, an aliphatic hydrocarbon group such as an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group or a dodecyl group, and an aromatic hydrocarbon group represented by the following general formula (9), but Not limited to this. It is preferably an ethyl group or a substituent represented by the following general formula (9).

【化12】

The reaction of such a polyfunctional epoxy polyoxyalkylene compound with at least one or more carboxylic acids can be carried out by a known method, for example, using an equimolar (meth)acrylic acid with respect to the epoxy group 1 molar. The reactant obtained by this reaction is an epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group. Further, the carboxylic acid containing at least one or more polymerizable double bonds in this case is an unsaturated carboxylic acid such as acrylic acid or methacrylic acid, hydroxyethyl acrylate represented by the following general formula (10), and hydroxyethyl methacrylate. a single polymerizable double bond obtained by reacting a hydroxyl group-containing (meth) acrylate such as an ester, polyethylene glycol monoacrylate or polyethylene glycol monomethacrylate with a dicarboxylic acid or the acid monoanhydride Esters.

【化13】

(wherein R ₃ is a hydrogen atom or a methyl group; R ₅ is a hydrocarbon group having 1 to 20 carbon atoms, and an etheric oxygen atom may be contained therein; and M is a divalent carboxylic acid residue).

Next, the alkali-soluble resin of the present invention represented by the general formula (1) represented by the reaction of the epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group with a dicarboxylic acid or the acid monoanhydride will be described. Production method.

First, the epoxy polyoxyalkylene compound described above is reacted with a carboxylic acid having at least one polymerizable double bond such as (meth)acrylic acid, and the obtained compound having a polymerizable double bond and a hydroxyl group (hereinafter referred to as epoxy) The (meth) acrylate compound is reacted with an acid component to obtain an alkali-soluble resin represented by the general formula (1). The reaction conditions relating to the solvent, the catalyst, and the like used at this time are not particularly limited. For example, a solvent having a boiling point higher than the reaction temperature may be used as a reaction solvent, such as ethyl cellosolve acetate. Solvent-based solvent such as butyl cellosolve acetate or high-boiling ether system such as diether, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate Or an ester solvent, or a ketone solvent such as cyclohexanone or diisobutyl ketone. Further, the catalyst to be used may, for example, be an ammonium salt such as tetraethylammonium bromide or triethylbenzylammonium chloride, or a phosphine such as triphenylphosphine or tris(2,6-dimethoxyphenyl)phosphine. Known things such as classes. This is described in detail in Japanese Laid-Open Patent Publication No. Hei 9-325494. Further, as the acid component, an acid monoanhydride obtained by reacting a hydroxyl group in a molecule of an epoxy (meth) acrylate compound can be used. As the acid monoanhydride, an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid, an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid, an acid anhydride of an aromatic dicarboxylic acid, or the like can be used. An anhydride of a saturated linear hydrocarbon dicarboxylic acid such as succinic acid, acetyl succinic acid, adipic acid, sebacic acid, cis malic acid, malonic acid, glutaric acid, citric acid, tartaric acid, carboxyglutaric acid An anhydride such as pimelic acid, sebacic acid, suberic acid or diglycolic acid, or a linear hydrocarbon dicarboxylic anhydride substituted with a hydrocarbon group. Further, an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid, such as an acid anhydride such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid or hexahydro trimellitic acid, An acid anhydride of an alicyclic dicarboxylic acid substituted with a saturated hydrocarbon. Further, an acid anhydride of an unsaturated dicarboxylic acid such as maleic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, methyl bridged methyltetrahydrofurfuric acid, chloric acid or trimellitic acid anhydride. Among these, the acid monoanhydride is preferably succinic acid, itaconic acid, tetrahydrofurfuric acid, hexahydrotrimellitic acid, citric acid, trimellitic acid anhydride, more preferably succinic acid, itaconic acid, or four. Hydrogen phthalic acid, trimellitic acid anhydride.

When the epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group is reacted with an acid component, the reaction temperature at the time of synthesizing the alkali-soluble resin represented by the general formula (1) is preferably from 20 to 140 ° C, more preferably 40 to 130 ° C. When the alkali-soluble resin represented by the general formula (1) is synthesized, the molar ratio of the acid mono-anhydride may be 10 to 10 in the epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group. 100% by mole. When the molar ratio of the acid mono-anhydride is adjusted for the acid value of the alkali-soluble resin represented by the above general formula (1), the above range can be arbitrarily changed.

Further, the photosensitive resin composition of the present invention is an alkali-soluble resin of the above general formula (1) for containing a main component of a resin component. The resin component means a component which becomes a resin by polymerization or hardening, for example, an epoxy resin, an acrylic resin or the like which is polymerized or cured by light or heat. Further, the resin component may contain an oligomer or a monomer other than the resin. Further, the content of the alkali-soluble resin of the general formula (1) containing the main component is 30% by weight or more, preferably 50% by weight or more, and more preferably 60% by weight or more based on the resin component. The photosensitive resin composition of the present invention contains an essential component which is an alkali-soluble resin represented by the general formula (1), and a component other than the resin of the general formula (1) is a resin component, or a solvent, a filler, and a coloring. Non-resin components such as agents.

In order to utilize the characteristics of the photosensitive resin composition, the essential components are the following components (i), (ii) and (iii). That is, the essential component is (i) an alkali-soluble resin having a carboxylic acid group and a polymerizable unsaturated group in one molecule represented by the general formula (1), and (ii) photopolymerization having at least one or more ethylenically unsaturated bonds. A monomer, (iii) a photopolymerization initiator.

A photopolymerizable monomer having at least one or more ethylenically unsaturated bonds of the component (ii), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- a monomer having a hydroxyl group such as ethylhexyl (meth) acrylate, or ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, or triethylene glycol di(meth)acrylic acid Ester, tetraethylene glycol di(meth)acrylate, tetramethyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tris(methyl) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, A (meth) acrylate such as glycerol (meth) acrylate. These compounds may be used alone or in combination of two or more.

The addition ratio [(i)/(ii)] of the component (ii) to the alkali-soluble resin [(i) component represented by the general formula (1) is 20/80 to 90/10, preferably 40/. 60 to 80/20. When the addition rate of the alkali-soluble resin is too small, the cured product after photohardening is embrittled, and the acid value of the coating film in the unexposed portion is lowered to lower the solubility with respect to the alkali developing solution, so that there is a pattern. The outline is not sharp enough. On the other hand, when the addition ratio of the alkali-soluble resin exceeds the above range, the crosslinking ratio of the photoreactive functional group in the resin is too small to sufficiently form a crosslinked structure, and the exposure is increased due to an excessively high acid value in the resin component. The solubility of the part relative to the alkali developing solution may cause a problem that the line width is too small and the pattern is not easily formed when the formed pattern is targeted.

Further, the photopolymerization initiator of the component (iii) is, for example, benzophenone, 2,2-diethoxydiphenylethanone, p-dimethoxybenzophenone, p-dimethylaminobenzene Acetone, benzophenone, trichloroacetophenone, p-tert-butylacetophenone, acetophenone, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethyl Benzophenones such as benzophenones, benzyl esters, benzoin, benzoin isobutyl ether, etc., 2-(o-chlorophenyl)-4,5-benzene Base imidazole, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)biimidazole, 2-(o-fluorophenyl)-4,5-diphenylbiimidazole , bi-imidazole-based compounds such as 2-(o-methoxyphenyl)-4,5-diphenylbiimidazole and 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-benzene Vinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5 -(p-methoxystyryl)-1,3,4-oxadiazole and other halomethyldiazole compounds, 2,4,6-tris(trichloromethyl)-1,3,5- Triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4- Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) )-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3, 4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxythiostyryl)-4,6- Halomethyl-s-triazine compounds such as bis(trichloromethyl)-1,3,5-triazine, 1,2-octanedione, 1-[4-(phenylthio)phenyl ]-2-(o-benzoquinone), 1-(4-(phenylthiophenyl)butane-1,2-dione-2-indole-o-benzoate, 1-(4) -methylsulfanylphenyl)butane-1,2-dione-2-indole-o-acetate, 1-(4-methylsulfanylphenyl)butan-1-one-oxime-o - o-mercapto lanthanide compounds such as acetate, benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthene Sulfides such as ketones and 2-isopropylthioxanthone, anthracene such as 2-ethyl fluorenone, octamethyl hydrazine, 1,2-benzopyrene, and 2,3-diphenyl hydrazine; Organic peroxides such as azobisisobutyronitrile, benzoquinone peroxide, cumene peroxide, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. Alcohol compound, triethanolamine, triethylamine grade 3 amine. These photopolymerization initiators may be used alone or in combination.

(iii) The amount of the photopolymerization initiator to be used is based on 100 parts by weight of the total of the alkali-soluble resin [(i) component] and the photopolymerizable monomer [(ii) component] represented by the general formula (1). It may be 2 to 50 parts by weight, preferably 15 to 40 parts by weight. When the addition ratio of the photopolymerization initiator relative to the component (ii) is too small, the photopolymerization rate is slowed down and the sensitivity is lowered. On the contrary, if the sensitivity is too strong, the pattern line width relative to the pattern mask is too wide, so the faithful line width relative to the mask cannot be reproduced, and the pattern outline is not sharp enough. problem. Further, the photopolymerization initiator of (iii) may contain a photo-sensitizing substance or a photo-sensitizer may be added in addition.

a photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1), a photopolymerizable monomer represented by the component (ii), and a photopolymerization initiator of the component (iii), which contains the component (i) as an essential component, It can be dissolved in a solvent if necessary, and various additives are added. That is, when the photosensitive resin composition of the present invention is used in a color filter or the like, it is preferred to use a solvent in addition to the above-mentioned essential components. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, and cyclohexanone. , ketones such as N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl Carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, three Glycol ether such as ethylene glycol monomethyl ether or triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve B Acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. By using these, a composition in a uniform solution can be obtained by dissolving and mixing.

Further, if necessary, an additive such as a curing accelerator, a thermal polymerization inhibiting agent, a plasticizer, a filler, a coating agent, or an antifoaming agent may be added to the photosensitive resin composition of the present invention. Among them, thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Plasticizers such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Fillers such as glass fiber, cerium oxide, mica, alumina, and the like. Further, an antifoaming agent and a coating agent such as a lanthanide, a fluorine-based or an acrylic compound.

The photosensitive resin composition of the present invention is preferably an alkali-soluble resin represented by the general formula (1) (i) in which the solid component (the solid component contains a monomer which becomes a solid component after hardening) after removal of the solvent, (ii) The total amount of the photopolymerizable monomer and the (iii) photopolymerization initiator is 70% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more. The amount of the solvent varies depending on the viscosity of the target, but is preferably from 20 to 80% by weight based on the total amount.

The photosensitive resin composition of the present invention can be used in addition to the above-mentioned alkali-soluble resin of the general formula (1), and other resin components which are polymerized or cured by light or heat can be used. Other resin components such as bisphenol A epoxy resin, phenol novolac epoxy resin, epoxy polyoxyalkylene resin epoxy resin, epoxy acrylate of bisphenol A epoxy resin, phenol novolak type Acrylic resin such as epoxy acrylate of epoxy resin, epoxy acrylate of epoxy polyoxyalkylene resin, poly(diallyl phthalate), poly(divinylbenzene), etc. containing allyl or ethylene Base resin and so on. In order to impart weather resistance, light resistance, and heat resistance, a polyoxyalkylene compound such as an epoxy polyoxyalkylene resin or an epoxy acrylate of an epoxy polyoxyalkylene resin is preferable.

In addition, the coating film (cured material) of the present invention can be obtained by applying a solution of the above-mentioned photosensitive resin composition to a predetermined substrate or the like, drying it, and then curing it by irradiation with light (including ultraviolet rays, radiation, or the like). After the illuminating portion and the non-illuminating portion are provided, only the illuminating portion is hardened, and when the other portion is dissolved in the alkali solution, the desired pattern coating film can be obtained.

Next, a pattern forming method using a photosensitive resin composition will be described. First, the photosensitive resin composition is applied onto the surface of a substrate or the like, and pre-baked to evaporate the solvent to form a coating film. Next, the coating film is exposed by a light mask, and then an alkaline developing solution is used to dissolve the unexposed portion of the coating film, and then baked to form a pattern.

When the photosensitive resin composition is applied to a substrate, any known methods such as a solution dipping method, a spray method, and other methods using a roll coater, a die coater, and a spin coater can be employed. After coating the desired thickness by these methods, the film is formed by removing the solvent (pre-baking). The pre-baking can be carried out by heating with an oven, a hot plate or the like, or by vacuum drying or combining them. The heating temperature and heating time of the pre-baking can be appropriately selected depending on the solvent to be used, for example, at 80 to 120 ° C for 1 to 20 minutes.

The radiation used in forming the pattern may be visible light, ultraviolet light, far ultraviolet light, electron light, X-ray or the like, and is preferably a radiation having a wavelength of 250 to 450 nm. Further, it is suitable for the alkali developing image developing solution such as an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, tetraethylammonium hydroxide, a tetrapropylammonium hydroxide aqueous solution, or the like. An amine such as ammonium hydroxide, diethylamine, triethylamine, diethanolamine or triethanolamine, in particular, a carbonate having a content of 0.05 to 10% by weight of sodium carbonate, potassium carbonate or lithium carbonate, and a hydrogen hydroxide can be used. A weakly alkaline aqueous solution of an ammonium hydroxide such as methylammonium or tetraethylammonium hydroxide or an amine such as diethylammonium or diethanolamine, which is commercially available at 20 to 30 ° C and or ultrasonically washed. A fine image can be precisely formed by a net machine or the like. After alkali imaging, it is generally washed with water. Suitable development methods include shower imaging, spray imaging, dipping (immersion) imaging, and stirring (liquid) imaging. The development condition is preferably 10 to 300 seconds at normal temperature.

After this development, heat treatment (post-baking) is carried out at a temperature of 180 to 250 ° C and a condition of 20 to 100 minutes. The purpose of this post-baking is to improve the adhesion between the patterned coating film and the substrate. It can be heated by an oven, a hot plate or the like as in the case of pre-baking. The patterned coating film of the present invention is formed through each step by the above-described photolithography method.

The substrate used in forming the pattern is, for example, glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfonate, etc.). Further, if necessary, these substrates can be subjected to an appropriate pretreatment such as drug treatment of a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction, or vacuum vapor deposition.

Example

Hereinafter, the present invention will be described in more detail by way of examples and the like of the alkali-soluble resin represented by the general formula (1). Further, the present invention is not limited to the embodiments and the like. Further, the evaluation of the resin in the following examples was carried out as follows unless otherwise specified.

[solid content concentration]

The filter glass [weight: W ₀ (g)] was impregnated with ₁ g of the resin solution (including the reaction product and the alkali-soluble resin) obtained in the examples (and comparative examples), and then weighed [W ₁ (g)], and then After heating at 160 ° C for 2 hours, the weight [W ₂ (g)] was determined by the following formula.

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

[epoxy equivalent]

After the resin solution was dissolved in dioxane, an acetic acid solution of tetraethylammonium bromide was added, and the mixture was titrated with a 1/10 N-perchloric acid solution using a potentiometric titration apparatus (trade name: COM-1600, manufactured by Hiranuma Seisakusho Co., Ltd.).

[acid price]

The resin solution was dissolved in dioxane, and titrated with a 1/10 N-KOH aqueous solution using a potentiometric titration apparatus (trade name: COM-1600, manufactured by Hiranuma Seisakusho Co., Ltd.).

[molecular weight]

The weight average molecular weight (Mw) in terms of standard polystyrene was determined by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

Further, the codes used in the examples and comparative examples are as follows.

FHPA: Equivalent reactant of bisphenol quinone type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid concentration: 50 wt%, acid value in solid content: 1.28 mg KOH/g)

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

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

TPP: triphenylphosphine

PGMEA: propylene glycol monomethyl ether acetate

[Example 1]

184 g of Si-H-based polydimethyl methoxyane (Si-H equivalent 363 g/eq), 250 g of dioxane, and platinum catalyst (platinum concentration 5%) 0.27 g attached to carbon powder were placed. Into a 1000 ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube, the internal temperature was raised to 90 ° C, and N-allyl-N',N"-diglycidyl isocyanuric acid was introduced in 3 hours. 150 g of ester. After the completion of the input, the internal temperature was raised to 110 ° C, and the mixture was heated and stirred while refluxing the dioxane. The reaction was dropped into a 0.1 N potassium hydroxide/methanol solution to confirm that hydrogen gas did not occur, and then the diatomaceous earth was added. The residual platinum catalyst is filtered, and the solvent of the filtrate is distilled off by an evaporator to obtain 320 g of an epoxy polyoxyalkylene resin (ES1) of the general formula (5). The obtained epoxy polyoxyalkylene resin is a general formula (5). Wherein p and n are both 0 having a linear decane bond and a hetero-cyanylene ring, and the terminal has an epoxy group. Further, the epoxy equivalent of the obtained epoxy polyoxyalkylene resin is 317 g/ Eq, viscosity is 4.5 Pa‧ s (25 ° C).

Next, 34.10 g (0.47 mol) of acrylic acid, 198.87 g of PGMEA, and 0.62 g of TPP were placed in 150 g of the above epoxy polyoxyalkylene resin in a 1000 ml four-necked flask equipped with a reflux tube, and stirred under heating at 100 to 105 ° C for 20 hours. Carry out the reaction. Further, THPA 53.49 g (0.35 mol) was placed in a flask, and stirred under heating at 120 to 125 ° C for 6 hours to obtain an alkali-soluble resin (i)-1. The obtained alkali-soluble resin had a solid content of 54.6 wt%, an acid value (in terms of solid content) of 85.3 mgKOH/g, and a Mw of 2540 from GPC analysis. Further, the obtained alkali-soluble resin showed a peak of 1,732 cm ^-1 (ester bond), 1409 cm ^-1 (vinyl group), and 1186 cm ^-1 (carboxyl group) from the IR measurement. Therefore, it was confirmed to be an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[Embodiment 2]

152 g of Si-H-based polydimethyloxane (Si-H equivalent 215 g/eq), 152 g of dioxane, and platinum catalyst (platinum concentration 5%) 0.36 g attached to carbon powder were placed. Into a 1000 ml four-necked flask equipped with a nitrogen introduction tube and a reflux tube, the internal temperature was raised to 90 ° C, and N-allyl-N',N"-diglycidyl isocyanurate was added in 3 hours. 200 g. After the completion of the input, the internal temperature was raised to 110 ° C, and the mixture was heated and stirred while refluxing the dioxane. The reaction was dropped into a 0.1 N potassium hydroxide/methanol solution to confirm that hydrogen gas did not occur, and then filtered with diatomaceous earth. The residual platinum catalyst is obtained by distilling off the solvent of the filtrate by an evaporator to obtain 324 g of the epoxy polyoxyalkylene resin (ES2) of the general formula (5). The obtained epoxy polyoxyalkylene resin is a general formula (5). The internal p and n are 0 and have a linear decane bond and an iso-cyanide ring, and have an epoxy group at the end. Further, the epoxy equivalent of the obtained epoxy polyoxynene resin is 237 g/eq. The viscosity is 0.34 Pa ‧ (25 ° C).

Next, 45.61 g (0.63 mol) of acrylic acid, 224.29 g of PGMEA and 0.83 g of TPP were placed in 150 g of the above epoxy polyoxyalkylene resin in a 1000 ml four-necked flask equipped with a reflux tube, and stirred under heating at 100 to 105 ° C for 20 hours. Carry out the reaction. Further, 72.22 g (0.47 mol) of THPA was placed in a flask, and stirred under heating at 120 to 125 ° C for 6 hours to obtain an alkali-soluble resin (i)-2. The obtained alkali-soluble resin had a solid content of 54.7 wt%, an acid value (in terms of solid content) of 101.1 mgKOH/g, and a Mw of 1800 from GPC analysis. Further, the obtained alkali-soluble resin showed a peak of 1730 cm ^-1 (ester bond), 1410 cm ^-1 (vinyl group), and 1188 cm ^-1 (carboxyl group) from the IR measurement. Therefore, it was confirmed to be an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[Comparative Example 1]

412.52g (0.34mol) of 50% PGMEA solution of FHPA, 50.02g (0.17mol) of BPDA, 25.87g (0.17mol) of THPA, 52.0g of PGMEA and 0.90g of TPP were placed in a 1000ml four-necked flask equipped with a reflux cooler. The mixture was stirred under heating at 120 to 125 ° C for 6 hours to obtain a resin (i)-3. The obtained resin solution had a solid content concentration of 55.6 wt%, an acid value (in terms of solid content) of 103.0 mgKOH/g, and a Mw of 2600 from GPC analysis. Further, the alkali-soluble resin obtained was observed to have a peak of 1,731 cm ^-1 (ester bond), 1407 cm ^-1 (vinyl group), and 1181 cm ^-1 (carboxyl group) from the IR measurement. Therefore, it was confirmed to be an alkali-soluble resin having a polymerized double bond and a carboxyl group.

Next, the present invention will be specifically described by way of examples and comparative examples for producing a photosensitive resin composition and a cured product thereof, but the present invention is not limited thereto. The raw material and code for producing the photosensitive resin composition and the cured product of the examples and the comparative examples are as follows.

(i)-1 component: the alkali-soluble resin obtained in the above Example 1.

(i)-2 component: the alkali-soluble resin obtained in the above Example 2

(i)-3 component: the alkali-soluble resin obtained in the above Comparative Example 1

(ii) Ingredients: dipentaerythritol hexaacrylate

(iii)-1 Ingredients: Photopolymerization initiator (Jilbas, Irkai 907)

(iii)-2 Ingredients: 4,4'-bis(diethylamino)benzophenone (photosensitizer)

(iv)-1 ingredient: tetramethylbiphenyl type epoxy resin

(iv)-2 component: epoxy polyoxyalkylene resin (ES2) obtained in Example 2.

Solvent-1: Propylene glycol monomethyl ether acetate

Solvent-2: dipropylene glycol dimethyl ether

Additive-1: decane coupling agent (SH-6040 made by Toray Island)

Additive-2: Surfactant (FC-430 manufactured by Sumitomo 3M Co., Ltd.)

The above-mentioned additive components were added in the ratio shown in Table 1, and the photosensitive resin compositions of Examples 3 to 5 and Comparative Example 2 were prepared. Further, the values in Table 1 are all parts by weight.

[Base imaging]

The photosensitive resin composition shown in Table 1 was baked by a spin coater, and then coated on a glass substrate of 125 mm × 125 mm under the conditions of a film thickness of 3.8 to 4.2 μm, and prebaked at 80 ° C for 3 minutes to prepare a coated plate. . Next, the photosensitive portion was subjected to photohardening reaction by irradiating ultraviolet rays with a high-pressure mercury lamp having an illuminance of 32 mJ/cm ² at a wavelength of 365 nm. Then, the coated plate after the end exposure is developed by dipping development in a 0.8 wt% aqueous solution of tetramethylammonium hydroxide at 23 ° C or an aqueous solution of 0.35 wt % diethanolamine at 23 ° C, and then washed with water to remove the coating. Unexposed portion of the film. Thereafter, it was dried by heating at 180 ° C for 90 minutes using a hot air dryer to obtain patterns of Examples 3 to 5 and Comparative Example 2.

The development of the pattern formed by the photosensitive resin compositions of Examples 3 to 5 and Comparative Example 2 obtained above, the development safety factor, and the like were evaluated. The results are shown in Table 2. These evaluation methods are as follows.

Film thickness: Measured using a stylus type step shape measuring device (trade name P-10 manufactured by Kenner Co., Ltd.).

Development time: The time required to completely dissolve the unexposed portion of the coating film during the alkali imaging was recorded, and was regarded as × even when the development time was over 300 seconds and the pattern could not be seen.

Tapered shape: The pattern after development is observed using a scanning electron microscope (manufactured by KEYENCE Co., Ltd., trade name VE-7800), and the cross-sectional shape of the pattern is regarded as ○, reverse cone or occurrence when maintaining a smooth and smooth shape. When peeling, it is regarded as ×.

Line shape: The length of the pattern portion of the 10 μm line after the development was evaluated by linearity or whisker using a length measuring microscope (manufactured by Nikon Co., Ltd., trade name: XD-20). It is considered to be ○ <good> when the linearity is good and does not occur, and is considered to be × <bad> when the linearity such as the edge is poor. When each item is very good, it is evaluated as ◎.

[Transmission rate]

Further, the photosensitive resin composition shown in Table 1 was baked by a spin coater, and then coated on a glass substrate of 125 mm × 125 mm under the conditions of a film thickness of 3.8 to 4.2 μm, and prebaked at 80 ° C for 3 minutes to prepare a coating. Layout. Next, the photocuring reaction was carried out by irradiating ultraviolet rays with a high-pressure mercury lamp having an illuminance of 32 mJ/cm ² at a wavelength of 365 nm. Subsequently, the film was dried by heating at 230 ° C for 30 minutes using a hot air dryer to obtain cured films of Examples 3 to 5 and Comparative Example 2. Thereafter, the transmittance of the obtained coated sheet was measured using a transmittance meter (trade name SPECTRO PHOTOMETER SD5000, manufactured by Nippon Denshoku Industries Co., Ltd.). When the transmittance at a wavelength of 380 nm was 90% or more, it was evaluated as ○, and when it was less than 90%, it was evaluated as ×.

[mechanical properties]

Further, the photosensitive resin composition shown in Table 1 was baked using a spin coater, and then coated on a 125 mm × 125 mm coated release agent aluminum substrate under the conditions of a film thickness of 28 to 32 μm, and pre-baked at 110 ° C. The coated plate was made in 10 minutes. Next, the photosensitive portion was subjected to a photohardening reaction by irradiating ultraviolet rays with a high-pressure mercury lamp having an illuminance of 32 mJ/cm ² at a wavelength of 365 nm. Subsequently, the coated plate after the end exposure was developed by dipping development in a 0.8 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C, and the unexposed portion of the coating film was removed by water washing. Thereafter, it was dried by heating at 180 ° C for 90 minutes using a hot air dryer. Further, the coated plate after the heat drying treatment was immersed in hot water at 80 ° C, and the cured film of Examples 3 to 5 and Comparative Example 2 was obtained by peeling off the coating film from the aluminum substrate. The glass transition point of the cured product was measured using a thermomechanical analyzer (EXSTAR 6000 manufactured by SII). When the glass transition point was 130 ° C or higher, it was regarded as ○, and when it was less than 130 ° C, it was regarded as ×. The results are shown in Table 3. Show.

From the results of the above Tables 2 and 3, it was found that the cured products of Examples 3 to 5 were excellent in performance, and in particular, the cured products of Examples 4 to 5 were able to maintain the same imaging and adhesion as Comparative Example 2. And a cured product having a higher transmittance can be formed. That is, it is possible to provide a cured film having weather resistance, light resistance, and heat resistance while maintaining alkali developability.

Industrial use possibility

The photosensitive resin composition of the present invention is a polysiloxane resin having weather resistance, light resistance and heat resistance, and is capable of forming weather resistance, light resistance and heat resistance. type. Therefore, it is applicable to various display elements such as a color liquid crystal display device, a color facsimile machine, and an image sensor, a color filter protective film material, a black matrix forming material, or a protective layer such as an organic device such as an organic semiconductor, a sealing agent, and the like. Agent.

Claims (6)

An alkali-soluble resin which is an alkali-soluble resin having a carboxylic acid residue and a polymerizable unsaturated group in one molecule, which is represented by the following general formula (1). (wherein R ₁ is a hydrocarbon group having 1 to 10 carbon atoms; R ₂ is a hydrocarbon group having 1 to 20 carbon atoms; the inside may contain an etheric oxygen atom; X is a divalent substituent which may contain a hetero atom internally; Y is a different a substituent having a polymerizable double bond and a carboxyl group bonded to the cyanuric acid ring skeleton; and Z is a substituent bonded to the hetero-cyanate ring skeleton containing a polymerizable double bond and a carboxyl group; m, n And p is independent from 0 to 100). An alkali-soluble resin according to the first aspect of the invention, wherein X in the general formula (1) is a divalent substituent represented by the general formula (2), Y is a substituent represented by the general formula (3), and Z is not The substituent in the case of a hydrogen atom is represented by the general formula (3), (wherein R ₃ is a hydrogen atom or a methyl group; R ₄ is a hydrocarbon group having 1 to 20 carbon atoms, and may have an etheric oxygen atom or an ester bond; R ₅ is a hydrocarbon group having 1 to 20 carbon atoms; and an ether may be contained therein; Oxygen atom; L is a substituent represented by the following general formula (4)) (wherein M is a 2 or 3 valent carboxylic acid residue; q is 1 or 2). An alkali-soluble resin as claimed in claim 1 or 2, which is represented by the following general formula (1') in which the n is 0 in the general formula (1) (wherein R ₁ is a hydrocarbon group having 1 to 10 carbon atoms; R ₂ is a hydrocarbon group having 1 to 20 carbon atoms; the inside may contain an etheric oxygen atom; X is a divalent substituent which may contain a hetero atom internally; Y is a different a substituent having a polymerizable double bond and a carboxyl group bonded to the cyanuric acid ring skeleton; Z is a hydrogen atom, or a substituent having a polymerizable double bond and a carboxyl group bonded to the heterocyanate ring skeleton ;m and p are independently 0 to 100). A photosensitive resin composition characterized by containing (i) an alkali-soluble resin having a carboxylic acid residue and a polymerizable unsaturated group in one molecule, which is represented by the following general formula (1); (wherein R ₁ is a hydrocarbon group having 1 to 10 carbon atoms; R ₂ is a hydrocarbon group having 1 to 20 carbon atoms; the inside may contain an etheric oxygen atom; X is a divalent substituent which may contain a hetero atom internally; Y is a different a substituent having a polymerizable double bond and a carboxyl group bonded to the cyanuric acid ring skeleton; Z is a hydrogen atom, or a substituent having a polymerizable double bond and a carboxyl group bonded to the heterocyanate ring skeleton m, n and p are independently from 0 to 100) (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator. The photosensitive resin composition of claim 4, wherein X in the general formula (1) is a divalent substituent represented by the general formula (2), and Y is a substituent represented by the general formula (3), and When Z is not a hydrogen atom, the substituent is represented by the general formula (3). (wherein R ₃ is a hydrogen atom or a methyl group; R ₄ is a hydrocarbon group having 1 to 20 carbon atoms, and may have an etheric oxygen atom or an ester bond; R ₅ is a hydrocarbon group having 1 to 20 carbon atoms; and an ether may be contained therein; Oxygen atom; L is a substituent represented by the following general formula (4)) (wherein M is a 2 or 3 valent carboxylic acid residue; q is 1 or 2). A cured product obtained by curing a photosensitive resin composition according to item 4 or 5 of the patent application.