WO2011024836A1 - Alkali-soluble resin containing silicone resin, light-sensitive resin composition, and cured object using light-sensitive resin composition - Google Patents

Abstract

Disclosed is an alkali-soluble silicone resin that can be used in a light-sensitive resin composition that has excellent weather resistance, light resistance, and heat resistance, and wherein the formation of micropatterns is possible. Further disclosed is a light-sensitive resin composition utilizing same. The alkali-soluble resin is represented by general formula 1 and has a carboxylic acid residue and a polymerizable unsaturated group in each molecule (R1 represents a hydrocarbon group that has 1-10 carbon atoms; R2 represents a hydrocarbon that has 1-20 carbon atoms; an ethereal oxygen atom may be contained inside X, which represents a bivalent substituent group that may contain a heteroatom inside, and Y, which represents a substituent group wherein a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton; Z represents a substituent group wherein a group containing a polymerizable double bond and a carboxyl group is bonded to a hydrogen atom or an isocyanuric ring skeleton; and m, n, and p independently represent a number from 0-100), and in addition to the abovementioned resin, the light-sensitive resin composition contains a photoinitiator and a photopolymerizable monomer having at least one ethylenically unsaturated bond.

Description

Alkali-soluble resin and photosensitive resin composition containing silicone resin, and cured product using photosensitive resin composition

The present invention relates to a photosensitive resin that is cured by irradiation with ultraviolet rays or an electron beam and that is alkali-soluble, a photosensitive resin composition including the photosensitive resin composition that can be patterned by alkali development, and the photosensitivity. The present invention relates to a cured product using a resin composition.

Silicone resins are excellent in electrical properties, adhesiveness, heat resistance, low water absorption, etc., and are used in many fields such as electronic materials. In particular, epoxy silicone resins having an epoxy group in the molecule are superior in weather resistance and light resistance compared to aromatic epoxy resins such as bisphenol A type diglycidyl ether and phenol novolac type epoxy resin. ) Useful as a sealing material. Specifically, it is possible to reduce deterioration and discoloration of the resin due to light and heat emitted from the LED element. However, these resins do not have a pattern forming ability by alkali development treatment and have limited applications.

Moreover, as a resin composition useful in the field of electronic materials such as LED encapsulants, for example, Patent Document 1 discloses a resin composition obtained by reacting a hydrogenated epoxy resin obtained by hydrogenating an aromatic epoxy resin and a polyvalent carboxylic acid. An alicyclic epoxy resin obtained by epoxidizing an epoxy resin having an epoxy equivalent of 230 to 1000 g / eq and a cyclic olefin, and an epoxy resin composition for sealing using the same are disclosed. Patent Document 2 discloses a silicone compound in which an isocyanuric acid compound having an epoxy group and a vinyl group and a silicone compound are added, and an isocyanuric acid having an epoxy group is introduced into the side chain. Patent Document 3 discloses a resin composition for a color filter protective film using an epoxy compound having a bisphenolfluorene skeleton. However, the compounds exemplified here do not have a pattern forming ability by alkali development.

On the other hand, 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 compounds exemplified here have an aromatic group, there is a concern about deterioration of the resin due to light or heat emitted from the LED or the like, and discoloration with time.

JP 2003-277473 A JP 2004-099751 A JP2004-69930 Patent No. 3455296

Therefore, as a result of intensive studies in order to solve the problems in the conventional resin composition as described above, the present inventors have obtained an epoxy silicone compound and a carboxylic acid containing a polymerizable double bond. It was found that an alkali-soluble silicone resin suitable for the formation of a photosensitive resin composition can be obtained by reacting the resulting polyhydric alcohol compound with dicarboxylic acid or its acid monoanhydride. And by using this alkali-soluble silicone resin, it succeeded in obtaining the photosensitive resin composition which provided alkali developability, maintaining the weather resistance, light resistance, and heat resistance which a silicone resin has.

Accordingly, an object of the present invention is to provide an alkali-soluble resin containing a silicone resin that is excellent in weather resistance, light resistance, heat resistance, etc. and can be used as a photosensitive resin composition capable of forming a fine pattern. .

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

Furthermore, another object of the present invention is to provide a cured product that is free from the risk of deterioration or discoloration due to light or heat.

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

(However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. A divalent substituent which may contain a hetero atom, Y represents a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton, and Z represents a hydrogen atom or an isocyanuric group. And a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the ring skeleton, m, n and p independently represent a number of 0 to 100.)

Moreover, this invention is alkali-soluble resin represented by the following general formula (1 ') whose n in the said General formula (1) is 0.

(However, R ₁ , R ₂ , X, and Z are the same as described above, and m and p independently represent a number of 0 to 100.)

Furthermore, the present invention provides (i) an alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in one molecule;

(However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. A divalent substituent which may contain a hetero atom, Y represents a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton, and Z represents a hydrogen atom or an isocyanuric group. And a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the ring skeleton, m, n and p independently represent a number of 0 to 100.)
A photosensitive resin composition comprising (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as essential components.

Preferred embodiments of the present invention are shown below. That is, X in the general formula (1) is a divalent substituent which may contain a hetero atom inside, preferably a divalent substituent represented by the following general formula (2). Is a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the isocyanuric ring skeleton, preferably a substituent represented by the following general formula (3), and Z is a hydrogen atom, Or a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the isocyanuric ring skeleton, and the substituent when Z is not a hydrogen atom is preferably represented by the following general formula (3) It is the photosensitive resin composition which mix | blends the said alkali-soluble resin and the said alkali-soluble resin as a component of (i).

(However, R ₃ represents a hydrogen atom or a methyl group. R ₄ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom or an ester bond. R ₅ represents a carbon number. A hydrocarbon group of 1 to 20 which may contain an etheric oxygen atom, and L represents a substituent represented by the following general formula (4).

(Wherein M represents a divalent or trivalent carboxylic acid residue, and q is 1 or 2)

A more preferred embodiment of the present invention is an alkali-soluble resin represented by the following general formula (1 ′) in which n in the general formula (1) is 0, and the alkali-soluble resin is used as the component (i). It is the photosensitive resin composition to mix | blend.

(However, R ₁ , R ₂ , X, and Z are the same as those in the general formula (1), and m and p independently represent a number of 0 to 100.)

The photosensitive resin composition of the present invention may be a photosensitive resin composition further containing the following components in addition to the components (i) to (iii).
(Iv) Epoxy resin or epoxy compound having two or more epoxy groups (where (iv) is an epoxy resin derived from phenols, an epoxy compound derived from an olefin compound containing a ring structure, and an epoxy having an isocyanuric skeleton) Compound or polyfunctional epoxy silicone resin)

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

The alkali-soluble resin represented by the general formula (1) of the present invention has high weather resistance, light resistance, and heat resistance compared to resins used in resin compositions conventionally 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 extremely useful as a color filter-related material, a protective layer for semiconductor devices and the like, a sealing material, and an adhesive.
In addition, since the photosensitive resin composition of the present invention contains an alkali-soluble resin represented by the general formula (1), weather resistance and light resistance compared to resin compositions conventionally used in the field of electronic materials and the like. And high heat resistance and 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 photosensitive resin composition of the present invention is extremely useful as a color filter-related material, a protective layer for semiconductor devices and the like, a sealing material, and an adhesive.

Hereinafter, the alkali-soluble resin and the photosensitive resin composition of the present invention will be described in detail.
In addition to having a photopolymerizable double bond derived from a polyhydric alcohol compound having a (meth) acryl group, the alkali-soluble resin represented by the general formula (1) has radical polymerizability, as will be described later. Since it contains an acidic group derived from acid monoanhydride, it has alkali solubility. The photosensitive resin composition of the present invention is a resin composition having properties as an alkali-developable photosensitive resin composition containing an alkali-soluble resin represented by the general formula (1) as a main component.

The alkali-soluble resin represented by the general formula (1) is obtained by reacting an epoxy group of an epoxy silicone compound with (meth) acrylic acid, and dihydric acid or its acid monoanhydride to the resulting polyhydric alcohol compound having a polymerizable double bond. It is a carboxyl group-containing silicone resin obtained by reacting a product. Since the alkali-soluble resin of the general formula (1) has both a polymerizable double bond and a carboxyl group, the alkali-developable photosensitive resin composition has excellent photocurability, good developability, and patterning characteristics.

The method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail. First, the alkali-soluble resin of the general formula (1) is a polymerization obtained by reacting the polyfunctional epoxy silicone compound represented by the general formula (5) with a carboxylic acid containing at least one polymerizable double bond. Derived from a polyhydric alcohol compound containing a double bond.

(However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. A divalent substituent which may contain a hetero atom, A represents a substituent in which an isocyanuric ring skeleton is bonded to a group containing an epoxy group, G represents a hydrogen atom or an isocyanuric ring skeleton, an epoxy group And a substituent containing a group containing m. M, n and p independently represent a number of 0 to 100.)

In the production of the alkali-soluble resin of the present invention, more preferably polymerization obtained by reacting the polyfunctional epoxy silicone compound represented by the general formula (6) with a carboxylic acid containing at least one polymerizable double bond Derived from a polyhydric alcohol compound containing a double bond.

(However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. G represents a divalent substituent which may contain a hetero atom, G represents a hydrogen atom or a substituent in which an isocyanuric ring skeleton is bonded to a group containing an epoxy group, and m and p are independently 0 to 100 Represents the number of

R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. These hydrocarbon groups include, for example, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, isobutyl groups, hexyl groups, octyl groups, isooctyl groups, linear hydrocarbon groups such as decyl groups, cyclohexyl groups, etc. An aromatic hydrocarbon group such as an aliphatic cyclic hydrocarbon group and a phenyl group are not limited to these and may be the same or different. A methyl group is preferred. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms and may contain an etheric oxygen atom inside. Examples of these hydrocarbon groups include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, a decylene group, a dodecylene group, or a divalent substituent represented by the following general formula (7). However, it is not limited to these, and they may be the same or different. A propylene group is preferred.

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

A in the general formula (5) represents a substituent in which a group containing an epoxy group is bonded to an isocyanuric ring skeleton. Advantageously -R ₇ -R ₈ - can be represented by (R _{9 -E) l.} Here, R ₈ is a group composed of an isocyanuric ring skeleton, and R ₇ and R ₉ are preferably a direct bond or a chain hydrocarbon group, but may contain a hetero atom. E is an epoxy group, and l is 1 to 2, preferably 2.

G in the general formula (5) represents a hydrogen atom or a substituent in which an isocyanuric ring skeleton is bonded to a group containing an epoxy group. In the case of substituents other than hydrogen atoms, preferably -R ₇ -R ₈ - can be represented by (R ₉ -E) _l. Here, R ₈ is a group composed of an isocyanuric ring skeleton, and R ₇ and R ₉ are preferably a direct bond or a chain hydrocarbon group, but may contain a hetero atom. E is an epoxy group, and l is 1 to 2, preferably 2. A preferred specific example is a substituent represented by the following general formula (8).

X in General formula (5) shows the bivalent substituent which may contain the hetero atom inside. Examples of these substituents include aliphatic hydrocarbon groups such as ethylene group, propylene group, butylene group, hexylene group, decylene group and dodecylene group, and aromatic hydrocarbon groups represented by the following general formula (9). However, it is not limited to these. An ethylene group or a substituent represented by the following general formula (9) is preferable.

For the reaction of such a polyfunctional epoxy silicone compound and a carboxylic acid containing at least one polymerizable double bond, a known method can be used. Performed using (meth) acrylic acid. The reaction product obtained by this reaction is an epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group. In this case, examples of the carboxylic acid containing at least one polymerizable double bond include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, hydroxyethyl acrylate as shown in the following general formula (10), and methacrylic acid. And monoesters having a polymerizable double bond obtained by a reaction of (meth) acrylate having a hydroxyl group such as hydroxyethyl acid, polyethylene glycol monoacrylate, and polyethylene glycol monomethacrylate with dicarboxylic acid or acid monoanhydride thereof. .

(However, R ₃ represents a hydrogen atom or a methyl group, R ₅ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom inside. M represents a divalent carboxylic acid residue. Group.)

Next, the method for producing an alkali-soluble resin of the present invention represented by the general formula (1) by reaction of an epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group, and dicarboxylic acid or its acid monoanhydride Will be explained.

First, a compound having a polymerizable double bond and a hydroxyl group obtained by reaction of the above-described epoxy silicone compound with a carboxylic acid containing at least one polymerizable double bond such as (meth) acrylic acid (hereinafter referred to as epoxy ( A (meth) acrylate compound) and an acid component are reacted to obtain an alkali-soluble resin represented by the general formula (1). There are no particular restrictions on the reaction conditions such as the solvent and catalyst used at this time. For example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the reaction solvent. Cellosolve solvents such as ethyl cellosolve acetate and butyl cellosolve acetate, high boiling point ether or ester solvents such as diglyme, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, cyclohexanone, diisobutyl ketone, etc. It may be a ketone solvent or the like. The catalyst used may be a known catalyst such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine. it can. These are described in detail in JP-A-9-325494. Moreover, as an acid component, it is good to use the acid monoanhydride which can react with the hydroxyl group in an epoxy (meth) acrylate compound molecule | numerator. Here, 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. Among these, examples of the acid anhydride of the saturated linear hydrocarbon dicarboxylic acid include succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelin. Examples thereof include anhydrides such as acid, sebacic acid, suberic acid, and diglycolic acid, and may also be linear hydrocarbon dicarboxylic acid anhydrides substituted with hydrocarbon groups. Examples of acid anhydrides of saturated cyclic hydrocarbon dicarboxylic acids include acid anhydrides such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and hexahydrotrimellitic acid. Further, an acid anhydride of an alicyclic dicarboxylic acid substituted with a saturated hydrocarbon may be used. Examples of the acid anhydride of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid acid anhydride. . Of these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, and trimellitic anhydride are preferable as acid monoanhydrides, and succinic acid, itaconic acid, tetrahydroacid are more preferable. It is an anhydride of phthalic acid and trimellitic acid.

The reaction temperature for synthesizing the alkali-soluble resin represented by the general formula (1) by reacting an epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group with an acid component is 20 to 140 ° C. The range is preferably 40 to 130 ° C. The molar ratio of the acid monoanhydride when synthesizing the alkali-soluble resin represented by the general formula (1) is 10 to 10 with respect to the hydroxyl group in the epoxy (meth) acrylate compound having a polymerizable double bond and a hydroxyl group. It should be 100 mol%. The molar ratio of the acid monoanhydride can be arbitrarily changed within the above range for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (1).

The photosensitive resin composition of the present invention contains the alkali-soluble resin represented by the general formula (1) as a main component of the resin component. Here, the resin component refers to a component that becomes a resin by being polymerized or cured, and examples thereof include an epoxy resin and an acrylic resin that are polymerized or cured by light or heat. The resin component includes an oligomer and a monomer in addition to the resin. Further, “containing as a main component” means that the alkali-soluble resin represented by the general formula (1) is contained in the resin component at 30 wt% or more, preferably 50 wt% or more, more preferably 60 wt% or more. The photosensitive resin composition of the present invention may contain an alkali-soluble resin represented by the general formula (1) as an essential component, and components other than the resin of the general formula (1) may be resin components, And non-resin components such as fillers and colorants.

In order to make use of the characteristics of the photosensitive resin composition, the following components (i), (ii) and (iii) are contained as essential components. (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) a photopolymerization having at least one ethylenically unsaturated bond. And (iii) a photopolymerization initiator as an essential component.

Among these, as the photopolymerizable monomer having at least one ethylenically unsaturated bond as component (ii), for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Monomers having a hydroxyl group such as ethylhexyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Mention may be made of (meth) acrylic acid esters such as intererythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and glycerol (meth) acrylate. These compounds can be used alone or in combination of two or more thereof.

The blending ratio [(i) / (ii)] of the component (ii) and the alkali-soluble resin [component (i)] represented by the general formula (1) is 20/80 to 90/10. Preferably, it is 40/60 to 80/20. When the blending ratio of the alkali-soluble resin is small, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so that the solubility in an alkali developer is lowered and the pattern edge is distorted. The problem of not getting sharp will occur. On the contrary, when the blending ratio of the alkali-soluble resin is larger than the above range, the ratio of the photoreactive functional group in the resin is small and the formation of the crosslinked structure is not sufficient, and the acid value in the resin component is too high, Since the solubility with respect to the alkaline developer in the exposed portion is increased, there is a possibility that the formed pattern becomes thinner than the target line width or the pattern is easily lost.

Examples of the photopolymerization initiator of component (iii) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butyl. Acetophenones such as acetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenyl Biimidazole, 2- (o-methoxyphenyl) -4,5- Biimidazole compounds such as phenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p Halomethyldiazole compounds such as -cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 2,4 , 6-Tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloro Methyl) -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 ( Lichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) ) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halomethyl-s-triazine compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2 -(O-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-o-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione O-acyloxime compounds such as -2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-one-oxime-o-acetate, benzyldimethyl ketal, thioxanthone, 2-chlorothioxan Son, 2,4-Diethylthioxanthone, 2-Methylthioxanthone, 2-Isopropylthioxanthone Sulfur compounds, 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, Examples thereof include thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. One or more of these photopolymerization initiators can be used.

The amount of the photopolymerization initiator used as the component (iii) is based on a total of 100 parts by weight of the alkali-soluble resin [component (i)] and the photopolymerizable monomer [component (ii)] represented by the general formula (1). 2 to 50 parts by weight, preferably 15 to 40 parts by weight. When the blending ratio of the photopolymerization initiator to the component (ii) is small, the speed of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, if the number is too large, the sensitivity is too strong and the pattern line width becomes thicker than the pattern mask, and the line width that is faithful to the mask cannot be reproduced, or the pattern edge does not rattle and become sharp. Problems may arise. Incidentally, the photopolymerization initiator (iii) includes those having a photosensitization effect, but it is possible to add a photosensitizer separately.

A photosensitive resin composition comprising, as essential components, an alkali-soluble resin represented by general formula (1) of component (i), a photopolymerizable monomer of component (ii), and a photopolymerization initiator of component (iii), If necessary, it can be dissolved in a solvent, or various additives can be blended. That is, when the photosensitive resin composition of the present invention is used for a color filter or the like, it is preferable to use a solvent in addition to the above essential components. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as 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, triethylene Glycol ethers such as recall monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether Examples thereof include acetates such as acetate and propylene glycol monoethyl ether acetate, and a uniform solution-like composition can be obtained by dissolving and mixing them.

In addition, additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, and an antifoaming agent can be blended with the photosensitive resin composition of the present invention as necessary. Among these, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

The photosensitive resin composition of the present invention comprises an alkali-soluble resin represented by the general formula (1) in (i) in a solid content excluding a solvent (the solid content includes a monomer that becomes a solid content after curing). It is desirable that the photopolymerizable monomer (ii) and (iii) the photopolymerization initiator in total contain 70 wt% or more, preferably 80 wt%, more preferably 90 wt% or more. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 20 to 80 wt% with respect to the total amount.

In the photosensitive resin composition of the present invention, other resin components that are polymerized or cured by light or heat may be used in combination as a resin component other than the alkali-soluble resin of the general formula (1). Other resin components include epoxy resins such as bisphenol A type epoxy resin, phenol novolac type epoxy resin, epoxy silicone resin, bisphenol A type epoxy resin epoxy acrylate, phenol novolac type epoxy resin epoxy acrylate, epoxy silicone resin epoxy Examples thereof include acrylic resins such as acrylate, allyl groups such as poly (diallyl phthalate), poly (divinylbenzene), and vinyl group-containing resins. In order to provide weather resistance, light resistance and heat resistance, silicone compounds such as epoxy silicone resins and epoxy acrylates of epoxy silicone resins are preferred.

The coating film (cured product) of the present invention is, for example, a solution of the photosensitive resin composition applied to a predetermined substrate or the like, dried, and irradiated with light (including ultraviolet rays and radiation). It is obtained by curing. A coating film having a desired pattern can be obtained by providing a portion that is exposed to light and a portion not exposed to light, curing only the portion that is exposed to light, and dissolving the other portion with an alkaline solution.

Next, a pattern forming method using the photosensitive resin composition will be described. First, after coating the photosensitive resin composition on the surface of a substrate or the like, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and forms a pattern by carrying out post-baking after that.

When applying the photosensitive resin composition to the substrate, any method such as a method using a roller coater machine, a land coater machine, or a spinner machine can be adopted in addition to a known solution dipping method and spray method. . After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent used, and for example, the heating is performed at a temperature of 80 to 120 ° C. for 1 to 20 minutes.

As the radiation used for forming the pattern, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 250 to 450 nm is preferable. Examples of the developer suitable for the alkali development include aqueous solutions of alkali metal or alkaline earth metal carbonates, aqueous solutions of alkali metal hydroxides, tetraethylammonium hydroxide, tetrapropylammonium hydroxide aqueous solutions, and the like. Ammonium hydroxides, amines such as diethylamine, triethylamine, diethanolamine, triethanolamine can be mentioned, but carbonates such as sodium carbonate, potassium carbonate, lithium carbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. It is better to develop at a temperature of 20 to 30 ° C. using a weak alkaline aqueous solution containing 0.05 to 10% by weight of an amine such as ammonium hydroxide, diethylamine or diethanolamine. Fine using a machine Images can be precisely formed a. In addition, it is usually washed with water after alkali development. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 10 to 300 seconds at room temperature.

After the development, heat treatment (post-bake) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-bake. The patterned coating film of this invention is formed through each process by the above photolithography method.

Examples of the substrate used when forming the pattern include glass and transparent films (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.). In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., as necessary. .

Hereinafter, the present invention will be described in more detail based on examples of the alkali-soluble resin represented by the general formula (1). The scope of the present invention is not limited by these examples. Moreover, evaluation of the resin in the following examples was performed as follows unless otherwise noted.

[Solid content]
1 g of the resin solution (including the reaction product and alkali-soluble resin) obtained in the examples (and comparative examples) was impregnated into a glass filter [weight: W ₀ (g)] and weighed [W ₁ ( g)], and the weight [W ₂ (g)] after heating at 160 ° C. for 2 hours, was obtained from the following equation.
Solid content concentration (% by weight) = 100 × (W ₂ −W ₀ ) / (W ₁ −W ₀ )

[Epoxy equivalent]
After dissolving the resin solution in dioxane, add acetic acid solution of tetraethylammonium bromide and titrate with 1 / 10N-perchloric acid solution using potentiometric titrator (trade name COM-1600 manufactured by Hiranuma Seisakusho Co., Ltd.). Asked.

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

[Molecular weight]
This is a value obtained by calculating the weight average molecular weight (Mw) as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent.

Abbreviations used in Examples and Comparative Examples are as follows.
FHPA: Equivalent reaction product of bisphenolfluorene type epoxy resin and acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd., ASF-400 solution: solid content concentration 50wt%, solid content converted acid value 1.28mgKOH / 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]
In a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube, 184 g of polydimethylsiloxane (Si-H equivalent 363 g / eq) having Si-H groups at both ends, 250 g of dioxane, and a platinum catalyst supported on carbon powder ( (Platinum concentration 5%) 0.27g was charged, the internal temperature was raised to 90 ° C, and 150g of N-allyl-N ', N "-diglycidyl isocyanurate was added over 3 hours. The mixture was heated to 110 ° C. and stirred while refluxing dioxane.The reaction solution was added dropwise to a 0.1N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated. The catalyst was filtered through Celite, and 320 g of the epoxy silicone resin (ES1) of the general formula (5) was obtained by distilling off the solvent of the filtrate with an evaporator. In the case where both p and n in 0) are 0 Having a chain siloxane bond and isocyanuric ring skeleton, and having an epoxy group at the terminal. The epoxy equivalent of the obtained epoxy silicone resin 317 g / eq, viscosity was 4.5Pa · s (25 ℃).

Next, in a 1000 ml four-necked flask with a reflux tube, 150 g of the above epoxy silicone resin was charged with 34.10 g (0.47 mol) of acrylic acid, 198.87 g of PGMEA, and 0.62 g of TPP, and stirred at 100 to 105 ° C. for 20 hours while heating. And reacted. Further, 53.49 g (0.35 mol) of THPA was charged into the flask and stirred at 120 to 125 ° C. for 6 hours with heating to obtain an alkali-soluble resin (i) -1. The obtained alkali-soluble resin had a solid content of 54.6 wt%, an acid value (converted to a solid content) of 85.3 mg KOH / g, and Mw by GPC analysis of 2540. From the IR measurement of the obtained alkali-soluble resin, peaks were observed at 1732 cm ⁻¹ (ester bond), 1409 cm ⁻¹ (vinyl group), and 1186 cm ⁻¹ (carboxyl group). This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[Example 2]
In a 1000 ml four-necked flask equipped with a nitrogen inlet tube and a reflux tube, 152 g of polydimethylsiloxane (Si-H equivalent 215 g / eq) having both ends Si-H groups, 152 g of dioxane, and a platinum catalyst supported on carbon powder ( (Platinum concentration 5%) 0.36g was charged, the internal temperature was raised to 90 ° C, and 200g of N-allyl-N ', N "-diglycidyl isocyanurate was added over 3 hours. The mixture was heated to 110 ° C. and stirred while refluxing dioxane.The reaction solution was added dropwise to a 0.1N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated. The catalyst was filtered through celite, and the solvent of the filtrate was distilled off with an evaporator to obtain 324 g of an epoxy silicone resin (ES2) of the general formula (5). In the case where both p and n in 0) are 0 Having a chain siloxane bond and isocyanuric ring skeleton, and having an epoxy group at the terminal. The epoxy equivalent of the obtained epoxy silicone resin 237 g / eq, viscosity was 0.34Pa · s (25 ℃).

Next, in a 1000 ml four-necked flask with a reflux tube, 150 g of the above epoxy silicone resin was charged with 45.61 g (0.63 mol) of acrylic acid, 224.29 g of PGMEA, and 0.83 g of TPP, and stirred at 100 to 105 ° C. for 20 hours while heating. And reacted. Further, 72.22 g (0.47 mol) of THPA was charged into the flask and stirred for 6 hours while heating at 120 to 125 ° C. 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 Mw by GPC analysis of 1800. From the IR measurement of the obtained alkali-soluble resin, peaks were observed at 1730 cm ⁻¹ (ester bond), 1410 cm ⁻¹ (vinyl group), and 1188 cm ⁻¹ (carboxyl group). This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

[Comparative Example 1]
412.52g (0.34mol) of FHPA 50% PGMEA solution, 50.02g (0.17mol) of BPDA, 25.87g (0.17mol) of THPA, 52.0g of PGMEA and TPP in a 1000ml four-necked flask with a reflux condenser Of 0.90 g and stirred at 120 to 125 ° C. for 6 hours with heating to obtain Resin (i) -3. The obtained resin solution had a solid content concentration of 55.6 wt%, an acid value (converted to a solid content) of 103.0 mg KOH / g, and Mw by GPC analysis of 2600. From the IR measurement of the obtained alkali-soluble resin, peaks were observed at 1731 cm ⁻¹ (ester bond), 1407 cm ⁻¹ (vinyl group), and 1181 cm ⁻¹ (carboxyl group). This confirmed that the resin was an alkali-soluble resin having a polymerizable double bond and a carboxyl group.

Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the production of the photosensitive resin composition and its cured product, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions and cured products thereof in the following Examples and Comparative Examples are as follows.

(i) -1 component: alkali-soluble resin obtained in Example 1 above
(i) -2 component: alkali-soluble resin obtained in Example 2 above
(i) -3 component: alkali-soluble resin obtained in Comparative Example 1 above
(ii) Component: Dipentaerythritol hexaacrylate
(iii) -1 component: photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 907)
(iii) -2 component: 4,4′bis (diethylamino) benzophenone (photosensitizer)
(iv) -1 component: Tetramethylbiphenyl type epoxy resin
(iv) -2 component: epoxy silicone resin (ES2) obtained in Example 2
Solvent-1: Propylene glycol monomethyl ether acetate solvent-2: Dipropylene glycol dimethyl ether additive-1: Silane coupling agent (SH-6040 manufactured by Toray Dow Corning)
Additive-2: Surfactant (FC-430 manufactured by Sumitomo 3M)

The above-described blending components were blended in the proportions shown in Table 1 to prepare photosensitive resin compositions of Examples 3 to 5 and Comparative Example 2. In addition, all the numerical values in Table 1 represent parts by weight.

[Alkali developability]
The photosensitive resin composition shown in Table 1 was applied to a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking would be 3.8 to 4.2 μm, and prebaked at 80 ° C. for 3 minutes. A coated plate was prepared. Thereafter, the photocuring reaction was carried out by irradiating ultraviolet rays with a high pressure mercury lamp having a wavelength of 365 nm and an illuminance of 32 mJ / cm ² . Next, this exposed coated plate is developed by dip development in a 0.8 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C or in a 0.35 wt% diethanolamine aqueous solution at 23 ° C, and further washed with water, Unexposed areas were removed. Thereafter, heat drying treatment was performed at 180 ° C. for 90 minutes using a hot air dryer, and patterns according to Examples 3 to 5 and Comparative Example 2 were obtained.

Table 2 shows the results of evaluating the developability, development margin, etc. of the patterns made of the photosensitive resin compositions of Examples 3 to 5 and Comparative Example 2 obtained above. These evaluation methods were performed as follows.

Film thickness:
Measurement was performed using a stylus type step shape measuring device (trade name P-10, manufactured by KLA-Tencor Corp.).

Development time:
During alkali development, the time required to dissolve all the unexposed parts of the coating film was recorded. When the pattern could not be seen even when the development time exceeded 300 seconds, it was marked as x.

Taper shape:
Observe the developed pattern using a scanning electron microscope (trade name VE-7800, manufactured by KEYENCE Corporation). If the pattern cross-section maintains a smooth forward taper, ○, reverse taper or peeling When x occurred, it was set as x.

Line shape:
With respect to the 10 μm line after development, the linearity of the pattern portion and the presence or absence of fringe were evaluated with a length measuring microscope (trade name: XD-20, manufactured by Nikon Corporation). Therefore, the case where the linearity was good and the fringe was not generated was evaluated as ○ <good>, and the case where the fringe was generated and the linearity was poor was evaluated as x <defect>. Each item was evaluated as ◎ only when it was very good.

 

[Transmissivity]
In addition, the photosensitive resin composition shown in Table 1 was applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking would be 3.8 to 4.2 μm, and at 80 ° C. for 3 minutes. Pre-baked to prepare a coated plate. This was followed by photocuring reaction by ultraviolet irradiation with a high pressure mercury lamp of the illuminance 32 mJ / cm ² with a wavelength of 365 nm. Thereafter, a heat drying treatment was performed at 230 ° C. for 30 minutes using a hot air dryer to obtain cured films according to Examples 3 to 5 and Comparative Example 2. The transmittance of the resulting coated plate was measured using a transmittance meter (trade name SPECTRO PHOTOMETER SD5000, manufactured by Nippon Denshoku Industries Co., Ltd.). In the case of, it evaluated as x.

[Mechanical properties]
Furthermore, the photosensitive resin composition shown in Table 1 was applied on an aluminum substrate coated with a 125 mm × 125 mm release agent using a spin coater so that the film thickness after post-baking was 28 to 32 μm. And prebaked at 110 ° C. for 10 minutes to prepare a coated plate. Thereafter, the photocuring reaction was carried out by irradiating ultraviolet rays with a high pressure mercury lamp having a wavelength of 365 nm and an illuminance of 32 mJ / cm ² . Next, this exposed coated plate was developed by dip development in a 0.8 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C., and further washed with water to remove unexposed portions of the coating film. Then, the heat drying process was performed for 90 minutes at 180 degreeC using the hot air dryer. Further, the coated plate after the heat drying treatment was immersed in hot water at 80 ° C., and the coating film was peeled off from the aluminum substrate to obtain cured films according to Examples 3 to 5 and Comparative Example 2. The glass transition point of the cured film is measured using a thermomechanical analyzer (EXSTAR 6000 manufactured by SII Co., Ltd.). When the glass transition point is 130 ° C or higher, X. The results are shown in Table 3.

 

As is clear from the results of Tables 2 and 3, the cured products according to Examples 3 to 5 are excellent in each performance. In particular, the cured products of Examples 4 to 5 are developed in the same manner as Comparative Example 2. Property and adhesion can be maintained, and further, a cured product having high transmittance can be formed. That is, it was found that a cured film having weather resistance, light resistance and heat resistance can be provided while maintaining alkali developability.

The photosensitive resin composition of the present invention forms a pattern having weather resistance, light resistance, and heat resistance by imparting photocurability and alkali developability to a silicone resin having weather resistance, light resistance, and heat resistance. can do. Therefore, various display elements such as color liquid crystal display devices, color facsimiles, image sensors, protective layers for color filter protective film materials and black matrix forming materials, or organic devices such as organic semiconductors, sealing materials, adhesives Can be suitably used.

Claims (6)

1. An alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in one molecule.
   

   

   
   (However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. A divalent substituent which may contain a hetero atom, Y represents a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton, and Z represents a hydrogen atom or an isocyanuric group. And a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the ring skeleton, m, n and p independently represent a number of 0 to 100.)
2. In general formula (1), X is a divalent substituent represented by general formula (2), Y is a substituent represented by general formula (3), and a substituent when Z is not a hydrogen atom. The alkali-soluble resin according to claim 1 represented by formula (3).
   

   

   
   
   

   

   
   (However, R ₃ represents a hydrogen atom or a methyl group. R ₄ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom or an ester bond. R ₅ represents a carbon number. A hydrocarbon group of 1 to 20 which may contain an etheric oxygen atom, and L represents a substituent represented by the following general formula (4).
   
   

   

   
   (Wherein M represents a divalent or trivalent carboxylic acid residue, and q is 1 or 2)
3. The alkali-soluble resin according to claim 1 or 2, which is represented by the following general formula (1 ') in which n in the general formula (1) is 0.
   

   

   
   (However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. Z represents a divalent substituent which may contain a hetero atom, Z represents a hydrogen atom or a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton, m and p Independently represents a number from 0 to 100.)
4. (I) an alkali-soluble resin represented by the following general formula (1) and having a carboxylic acid residue and a polymerizable unsaturated group in one molecule;
   

   

   
   (However, R ₁ represents a hydrocarbon group having 1 to 10 carbon atoms. R ₂ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom. A divalent substituent which may contain a hetero atom, Y represents a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to an isocyanuric ring skeleton, and Z represents a hydrogen atom or an isocyanuric group. And a substituent in which a group containing a polymerizable double bond and a carboxyl group is bonded to the ring skeleton, m, n and p independently represent a number of 0 to 100.)
   A photosensitive resin composition comprising (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as essential components.
5. In general formula (1), X is a divalent substituent represented by general formula (2), Y is a substituent represented by general formula (3), and a substituent when Z is not a hydrogen atom. The photosensitive resin composition of Claim 4 represented by Formula (3).
   

   

   
   
   

   

   
   (However, R ₃ represents a hydrogen atom or a methyl group. R ₄ represents a hydrocarbon group having 1 to 20 carbon atoms, and may contain an etheric oxygen atom or an ester bond. R ₅ represents a carbon number. A hydrocarbon group of 1 to 20 which may contain an etheric oxygen atom, and L represents a substituent represented by the following general formula (4).
   
   

   

   
   (Wherein M represents a divalent or trivalent carboxylic acid residue, and q is 1 or 2)
6. A cured product obtained by curing the photosensitive resin composition according to claim 4 or 5.