JP2011209442A - Photosensitive alkali-soluble resin composition containing cyclic silicone resin, and cured product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is superior in weatherability, light and heat resistances and enables a fine pattern to be formed.SOLUTION: The photosensitive resin composition contains, as the essential components (i), a photosensitive alkali-soluble resin represented by general formula (1) and having a carboxyl group and a polymerizable unsaturated group within one molecule (wherein Ris a 1-10C hydrocarbon group; Rdenotes a 1-20C hydrocarbon group and may internally contain an etheric oxygen atom; X is a substituent having an isocyanuric ring containing a polymerizable double bond and a carboxyl group; and n represents a number of 3-6), (ii) a photopolymerizable monomer, having at least one ethylenically unsaturated bond and (iii) a photopolymerization initiator.

Description

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

  Silicone resins are excellent in electrical properties, adhesiveness, heat resistance, low water absorption, etc., and are used in many fields such as the electronic material field. 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, none of the compounds exemplified herein has the ability to form a pattern by alkali development.

  On the other hand, Patent Document 4 discloses an alkali-soluble aromatic resin compound for color filters 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. 3509269

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

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

〔但し、Ｒ₁は炭素数１〜１０の炭化水素基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｘは一般式（２）で示される置換基であり、Ｘ₁及びＸ₂はそれぞれ重合性二重結合を含み、少なくとも一方はカルボキシル基を含む。ｎは３〜６の数を表す。〕

（ii）少なくとも１個以上のエチレン性不飽和結合を有する光重合性モノマー、及び
（iii）光重合開始剤
を必須の成分として含有することを特徴とする感光性樹脂組成物である。 That is, the present invention provides (i) a photosensitive alkali-soluble resin represented by the following general formula (1) and having a carboxyl group 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 inside. X is a substituent represented by the general formula (2), and X ₁ and X ₂ each contain a polymerizable double bond, and at least one of them contains a carboxyl group. n represents the number of 3-6. ]

A photosensitive resin composition comprising (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as essential components.

（但し、Ｒ₃は水素原子又はメチル基を示す。Ｒ₄は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子、又はエステル結合を含んでいても良い。Ｒ₅は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｌは下記一般式（４）で表される置換基、又は水素原子を示す。）

（但し、Ｍ₁は２または３価のカルボン酸残基を示し、ｑは１または２である） Preferred embodiments of the present invention are shown below. That is, X in the general formula (1) is the photosensitive alkali-soluble resin composition, which is preferably a substituent represented by the following general 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 carbon. 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) or a hydrogen atom.

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

  Moreover, in addition to the said (i)-(iii) component, this invention is good also as the photosensitive resin composition containing the other resin component further superposed | polymerized or hardened | cured by light or a heat | fever. Examples of the other resin component include an epoxy resin having two or more epoxy groups.

  Furthermore, this invention is a hardened | cured material obtained by apply | coating the said photosensitive resin composition and making it harden | cure.

  The photosensitive resin composition containing the photosensitive alkali-soluble resin represented by the general formula (1) of the present invention has a weather resistance, a light resistance, and a resin composition conventionally used in the field of electronic materials and the like. High heat resistance and alkali developability. That is, a cured product excellent in 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 photosensitive resin composition of the present invention will be described in detail.
As described later, the photosensitive alkali-soluble resin represented by the general formula (1) of the present invention is a carboxyl group of a carboxylic acid containing at least one polymerizable double bond in the epoxy group of the polyfunctional epoxy resin. In addition to having photocurability derived from the polyhydric alcohol compound formed by bonding, the polyhydric alcohol compound contains an acidic group derived from the reaction of acid monoanhydride. Have.

  The photosensitive alkali-soluble resin of the general formula (1) contains at least one polymerizable double bond in an epoxy group of a polyfunctional epoxy cyclic silicone compound (hereinafter sometimes simply referred to as “epoxy cyclic silicone compound”). A dicarboxylic acid or an acid monoanhydride thereof is reacted with the resulting polyhydric alcohol compound having a polymerizable double bond (hereinafter sometimes referred to as “epoxy acrylate cyclic silicone compound”). It is an epoxy acrylate cyclic silicone resin containing a carboxyl group, obtained by reaction. Since the photosensitive alkali-soluble resin of the general formula (1) has both a polymerizable double bond and a carboxyl group, it has excellent photocurability, good developability, and patterning when it is used as an alkali-developable photosensitive resin composition. Give properties.

（但し、Ｒ₁は炭素数１〜１０の炭化水素基を示す。Ｒ₂は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｙはイソシアヌル環骨格に、エポキシ基を含んだ基が結合した置換基を示す。ｎは３〜６の数を表す。） A method for producing the photosensitive alkali-soluble resin represented by the general formula (1) will be described in detail. First, an epoxy cyclic silicone compound represented by the general formula (5) is reacted with a carboxylic acid containing at least one polymerizable double bond to synthesize an epoxy acrylate cyclic silicone compound.

(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. Y is an isocyanuric ring. A substituent in which a group containing an epoxy group is bonded to the skeleton is shown, and n represents a number of 3 to 6.

（但し、Ｒ₆は炭素数１〜１７の炭化水素基又は単結合である。） Here, R ₁ in the general formula (5) is a hydrocarbon group having 1 to 10 carbon atoms. Examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Groups, hexyl groups, octyl groups, isooctyl groups, linear hydrocarbon groups such as decyl groups, alicyclic hydrocarbon groups such as cyclohexyl groups, and aromatic hydrocarbon groups such as phenyl groups. They may be the same or different. Of these, 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 such a hydrocarbon group 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 (5). However, it is not limited to these, and they may be the same or different. Of these, a propylene group is preferred.

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

Moreover, Y in General formula (5) shows the substituent which the group containing the epoxy group couple | bonded with the isocyanuric ring frame | skeleton, Preferably, it can represent with -R < ₇ >-(R < ₈ > -E) ₂ . Here, R ₇ is a group comprising an isocyanuric ring skeleton, and R ₈ is preferably a direct bond or a chain hydrocarbon group, but may contain an etheric oxygen atom inside. E is an epoxy group. About this preferable Y, the substituent represented by the following general formula (7) can be illustrated as a specific example.

（但し、Ｒ₃は水素原子又はメチル基を示し、Ｒ₉は炭素数１〜２０の炭化水素基を示し、内部にエーテル性酸素原子を含んでいても良い。Ｍ₂は２価のカルボン酸残基を示す。） For the reaction of such an epoxy cyclic silicone compound with a carboxylic acid containing at least one polymerizable double bond, a known method can be used. For example, for 1 mol of epoxy groups in the cyclic silicone compound, The reaction is carried out by reacting 1 mol of a carboxyl group of a carboxylic acid containing at least one polymerizable double bond. The reaction product obtained by this reaction is an epoxy acrylate cyclic silicone 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, and acrylic acid represented by the following general formula (8). Dicarboxylic acid having a polymerizable double bond obtained by reaction of (meth) acrylate having a hydroxyl group such as hydroxyethyl, hydroxyethyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate and the like with dicarboxylic acid or its acid monoanhydride These monoesters are also included.

(However, R < ₃ > shows a hydrogen atom or a methyl group, R < ₉ > shows a C1-C20 hydrocarbon group, and may contain the etheric oxygen atom inside. M < ₂ > is bivalent carboxylic acid. Indicates a residue.)

  Next, the reaction of the epoxy acrylate cyclic silicone compound having a polymerizable double bond and a hydroxyl group obtained above with a dicarboxylic acid or an acid monoanhydride of the present invention represented by the general formula (1) A method for obtaining a photosensitive alkali-soluble resin will be described.

    That is, the photosensitive alkali-soluble resin represented by the general formula (1) is obtained by reacting the acid component with the hydroxyl group of the epoxy acrylate cyclic silicone compound. At this time, the reaction conditions such as a solvent and a catalyst to be used are not particularly limited. 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 is preferable to use a ketone solvent. 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.

    As the acid component, it is preferable to use an acid monoanhydride capable of reacting with a hydroxyl group in the epoxy acrylate compound molecule, an acid anhydride of a saturated linear hydrocarbon dicarboxylic acid, an acid anhydride of a saturated cyclic hydrocarbon dicarboxylic acid. And acid anhydrides of unsaturated dicarboxylic acids 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 unsaturated dicarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, and trimellitic acid. Among these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid, or trimellitic anhydride is preferable, and succinic acid, itaconic acid, tetrahydrophthalic acid are more preferable. It may be an acid or an anhydride of trimellitic acid.

  The reaction temperature when synthesizing the photosensitive alkali-soluble resin represented by the general formula (1) by reacting the epoxy acrylate cyclic silicone compound with the acid component is preferably in the range of 20 to 140 ° C, more preferably. 40-130 ° C. The molar ratio of the acid monoanhydride when synthesizing the alkali-soluble resin represented by the general formula (1) is preferably 10 to 100 mol% with respect to the hydroxyl group in the epoxy acrylate cyclic silicone compound. The molar ratio of the acid monoanhydride is determined for the purpose of adjusting the acid value of the photosensitive alkali-soluble resin represented by the general formula (1), and can be arbitrarily changed within the above range.

  The photosensitive resin composition of this invention contains the photosensitive alkali-soluble resin of the said General formula (1) as a main component of a 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 photosensitive alkali-soluble resin of 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 a photosensitive 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. Non-resin components such as solvents, fillers and colorants may also be used.

  In order to take advantage of the characteristics as the photosensitive resin composition, the following components (i), (ii) and (iii) are contained as essential components. That is, (i) a photosensitive alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (1), (ii) having at least one ethylenically unsaturated bond A photopolymerizable monomer and (iii) a photopolymerization initiator are contained as essential components.

  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, pen Examples include (meth) acrylic acid esters such as taerythritol 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.

  About the compounding ratio [(i) / (ii)] of these (ii) component and the photosensitive alkali-soluble resin [component (i)] represented by the general formula (1), 20/80 to 90/10 And preferably 40/60 to 80/20. When the blending ratio of the photosensitive 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 reduced. There is a problem that it does not become sharp due to rattling. On the contrary, when the blending ratio of the photosensitive 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. As a result, the solubility of the exposed portion in the alkaline developer is increased, which may cause a problem 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-diphenylbiimidazole, biimidazole compounds such as 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloro Halomethylthiazole compounds such as methyl-5- (p-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 (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 (trichloroRmethyl) -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- ( Halomethyl-s-triazine compounds such as 4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 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-2-oxime-o-acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-o-acetate, etc., o-acyloxime compounds, benzyldimethyl ketal, thioxanthone, 2-chloro Thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxone Organic compounds such as sulfur compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, etc. Products, 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 100 parts by weight in total of the photosensitive 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 with respect to the sum of the components (i) and (ii) is small, the speed of photopolymerization is slowed 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 photosensitizing action, but it is possible to add a photosensitizer separately.

  A photosensitive resin composition comprising, as essential components, a photosensitive alkali-soluble resin represented by general formula (1) of component (i), a photopolymerizable monomer of component (ii), and a photopolymerization initiator of component (iii). Can be dissolved in a solvent or mixed with various additives as necessary. 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.

  Moreover, additives, such as a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoamer, can be mix | blended with the photosensitive resin composition of this invention as needed. 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. Examples of the filler include glass fiber, silica, mica, and alumina. Examples of leveling agents and antifoaming agents include silicon-based, fluorine-based, and acrylic compounds.

  The photosensitive resin composition of the present invention contains a photosensitive alkali 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 total amount of the soluble resin, the photopolymerizable monomer (ii), and the (iii) photopolymerization initiator is 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 10 to 30 wt% with respect to the total amount.

  In the photosensitive resin composition of the present invention, as the resin component other than the photosensitive alkali-soluble resin of the general formula (1), other resin components that are polymerized or cured by light or heat may be used in combination. 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 cured product (coating film) 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 cured product having a desired pattern can be obtained by providing a portion that is exposed to light and a portion that is not irradiated, 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 coating 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 to be used, and are performed, for example, 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 good to develop at a temperature of 20 to 30 ° C. using a weak alkaline aqueous solution containing 0.05 to 10% by weight of amines such as ammonium hydroxide, diethylamine and 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 as described above, a 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 cured product of the present invention is formed through each step by the above photolithography method.

  Examples of the substrate used for 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 photosensitive resin composition of the present invention will be described in more detail while specifically showing synthesis examples of the photosensitive alkali-soluble resin represented by the general formula (1) used in the examples of the present invention. . The scope of the present invention is not limited by these synthesis examples. Moreover, evaluation of the resin in the following synthesis examples etc. was performed as follows unless otherwise noted.

[Solid content]
1 g of the resin solution (including reaction products and alkali-soluble resins) obtained in the synthesis examples (and comparative synthesis 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 the synthesis examples and comparative synthesis 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 50 wt%, solid content converted acid value 1.28 mgKOH / g)
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

[Synthesis Example 1]
In a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux tube, 48 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 480 g of dioxane, and 0.04 g of platinum catalyst supported on carbon powder (platinum concentration 5%) After charging, the internal temperature was raised to 90 ° C., and then 224 g of N-allyl-N ′, N ”-diglycidyl isocyanurate was added over 3 hours. After completion of the addition, the temperature was raised to a temperature at which dioxane began to reflux. The reaction solution was added dropwise to a 0.1 N potassium hydroxide / methanol solution, and it was confirmed that hydrogen gas was not generated, and the remaining platinum catalyst was filtered through Celite. The solvent of the liquid was distilled off to obtain 240 g of an epoxy cyclic silicone resin (CES1) of the general formula (5), wherein R ₁ in the general formula (5) is a methyl group, and n is 4 with a ring The epoxy cyclic silicone resin had an epoxy equivalent of 174 g / eq and a viscosity of 0.5 Pa · s (150 ° C). .

Next, in a 1000 ml four-necked flask equipped with a reflux tube, with respect to 150 g of the above epoxy cyclic silicone resin, 61.97 g (0.86 mol) of acrylic acid, 259.57 g of PGMEA, and 0.57 g of TPP were charged at 100 to 105 ° C. The reaction was stirred for 20 hours under heating. Furthermore, 98.37 g (0.65 mol) of THPA was charged into the flask and stirred for 6 hours while heating at 120 to 125 ° C. to obtain photosensitive alkali-soluble resin (i) -1. The obtained photosensitive alkali-soluble resin had a solid content of 54.9 wt%, an acid value (in terms of solid content) of 121.2 mgKOH / g, and Mw by GPC analysis of 2230. From the IR measurement of the obtained alkali-soluble resin, peaks were observed at 1731 cm ⁻¹ (ester bond), 1410 cm ⁻¹ (vinyl group), and 1188 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

[Comparative Synthesis Example 1]
Platinum catalyst supported on carbon powder with 184 g of polydimethylsiloxane (SI-H equivalent 363 g / eq) with Si-H groups at both ends, 250 g of dioxane, and carbon powder in a 1000 ml four-necked flask with a nitrogen inlet tube and a reflux tube (Platinum concentration 5%) 0.27 g was charged, the internal temperature was raised to 90 ° C., and then 150 g of N-allyl-N ′, N ″ -diglycidyl isocyanurate was added over 3 hours. The temperature was raised to 110 ° C., and the mixture was heated 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 platinum catalyst was filtered through Celite, and 320 g of the epoxy silicone resin (ES1) of the general formula (9) was obtained by distilling off the solvent of the filtrate with an evaporator. (9) R ₁ in is a methyl group, 8 has a linear siloxane skeleton and an isocyanuric ring skeleton, and has an epoxy group at the terminal, and the epoxy silicone resin thus obtained has an epoxy equivalent of 317 g / eq and a viscosity of 4.5 Pa · s (25 ° C. )Met.

Next, in a 1000 ml four-necked flask equipped with a reflux tube, with respect to 150 g of the epoxy silicone resin, was charged 34.10 g (0.47 mol) of acrylic acid, 198.87 g of PGMEA, and 0.62 g of TPP and heated at 100 to 105 ° C. The reaction was stirred for 20 hours below. Further, 53.49 g (0.35 mol) of THPA was charged into the flask and stirred for 6 hours under heating at 120 to 125 ° C. to obtain photosensitive alkali-soluble resin (i) -2. The obtained photosensitive 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 photosensitive alkali-soluble resin, peaks were observed at 1732 cm ⁻¹ (ester bond), 1409 cm ⁻¹ (vinyl group), and 1186 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

[Comparative Synthesis Example 2]
Platinum catalyst supported on carbon powder by 152g of polydimethylsiloxane (SI-H equivalent 215g / eq) with Si-H groups at both ends, 152g of dioxane, and carbon powder in a 1000ml four-necked flask with nitrogen inlet and reflux tube (Platinum concentration: 5%) 0.36 g was charged and the internal temperature was raised to 90 ° C., and then 200 g of N-allyl-N ′, N ″ -diglycidyl isocyanurate was added over 3 hours. The temperature was raised to 110 ° C., and the mixture was heated 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 platinum 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 (9). (9) R ₁ in is a methyl group, 4 has a linear siloxane skeleton and an isocyanuric ring skeleton, and has an epoxy group at the terminal, and the epoxy silicone resin thus obtained has an epoxy equivalent of 237 g / eq and a viscosity of 0.34 Pa · s (75 ° C. )Met.

Next, in a 1000 ml four-necked flask with a reflux tube, 45.61 g (0.63 mol) of acrylic acid, 224.29 g of PGMEA, and 0.83 g of TPP are charged to 150 g of the above epoxy silicone resin and heated at 100 to 105 ° C. The reaction was stirred for 20 hours below. 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 photosensitive alkali-soluble resin (i) -3. The obtained photosensitive 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 an Mw of 1800 by GPC analysis. From the IR measurement of the obtained photosensitive alkali-soluble resin, peaks were observed at 1730 cm ⁻¹ (ester bond), 1410 cm ⁻¹ (vinyl group), and 1188 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

[Comparative Synthesis Example 3]
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 0.90 g was added and stirred at 120 to 125 ° C. for 6 hours with heating to obtain photosensitive alkali-soluble resin (i) -4. The obtained resin solution had a solid content concentration of 55.6 wt%, an acid value (in terms of solid content) of 103.0 mg KOH / g, and Mw by GPC analysis of 2600. From the IR measurement of the obtained photosensitive alkali-soluble resin, peaks were observed at 1731 cm ⁻¹ (ester bond), 1407 cm ⁻¹ (vinyl group), and 1181 cm ⁻¹ (carboxyl group). From this, it confirmed that it was a photosensitive alkali-soluble resin which has a polymerizable double bond and a carboxyl group.

  Next, although this invention is demonstrated concretely based on the Example and comparative example which concern on manufacture of the photosensitive resin composition and its hardened | cured material, this invention is not limited to these. 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: photosensitive alkali-soluble resin obtained in Synthesis Example 1 above
(i) -2 component: photosensitive alkali-soluble resin obtained in Comparative Synthesis Example 1 above
(i) -3 component: photosensitive alkali-soluble resin obtained in Comparative Synthesis Example 2
(i) -4 component: photosensitive alkali-soluble resin obtained in Comparative Synthesis Example 3
(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 cyclic silicone resin (CES1) obtained in Synthesis Example 1
(iv) -3 component: epoxy silicone resin (ES2) obtained in Comparative Synthesis 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 said component was mix | blended in the ratio shown in Table 1, and the photosensitive resin composition of Example 1 and Comparative Examples 1-4 was prepared. In addition, all the numerical values in Table 1 represent parts by weight.

[Alkali developability]
The photosensitive resin composition shown in Table 1 is applied on a 125 mm × 125 mm glass substrate using a spin coater so that the film thickness after post-baking is 3.8 to 4.2 μm, and prebaked at 80 ° C. for 3 minutes. A coated plate was prepared. Thereafter, UV irradiation with a illuminance of 32 mJ / cm ² having a wavelength of 365 nm was performed with a 500 W / cm ² high-pressure mercury lamp to carry out a photocuring reaction of the photosensitive portion. 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. Then, the pattern which concerns on Example 1 and Comparative Examples 1-4 was obtained by heat-drying for 90 minutes at 180 degreeC using a hot air dryer.

  Table 2 shows the results of evaluating developability, development margin, and the like for the patterns made of the photosensitive resin compositions of Example 1 and Comparative Examples 1 to 4 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 In the case where the cross-sectional shape of the pattern occurred, it was marked 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.

The tackiness of the coating surface:
The tackiness of the coating surface prepared by prebaking at 80 ° C. for 3 minutes was evaluated. The case where there was no tackiness was marked as ◯, the case where there was a slight tackiness, Δ, and the case where there was marked tackiness, ×.

Coating film shrinkage:
The film thickness [thickness: T ₀ (μm)] of the coating film after development and the film thickness [thickness: T ₁ (μm)] after heat drying at 180 ° C. for 90 minutes were determined from the following formula. . When the contraction rate of the coating film was 10% or more, ×, when 5 to 10%, ○, and when it was 5% or less, ◎.
Coating film shrinkage (%) = 100 × (1−T ₁ / T ₀ )

[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. Thereafter, UV curing with a illuminance of 32 mJ / cm ² having a wavelength of 365 nm was performed by a 500 W / cm ² high-pressure mercury lamp to carry out a photocuring reaction. Then, the cured film which concerns on Example 1 and Comparative Examples 1-4 was obtained by heat-drying for 30 minutes at 230 degreeC using a hot air dryer. Then, the transmittance of the obtained coated plate was measured using a transmittance meter (trade name SPECTRO PHOTOMETER SD5000, manufactured by Nippon Denshoku Industries Co., Ltd.), and when the transmittance at a wavelength of 380 nm was 90% or more, less than 90% In the case of, it was evaluated as x.

[Mechanical properties]
Further, 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, UV irradiation with a illuminance of 32 mJ / cm ² having a wavelength of 365 nm was performed with a 500 W / cm ² high-pressure mercury lamp to carry out a photocuring reaction of the photosensitive portion. 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. Furthermore, the coated plate after the heat drying treatment was immersed in hot water at 80 ° C., and the coating film was peeled from the aluminum substrate to obtain cured films according to Example 1 and Comparative Examples 1 to 4. Then, the glass transition point of the cured film was measured using a thermomechanical analyzer (EXSTAR 6000 manufactured by SII Co., Ltd.), and when the glass transition point was 160 ° C. or higher, ◎, 145 ° C. to 160 ° C. ◯ in the case, Δ in the case of 130 ° C to 145 ° C, and x in the case of less than 130 ° C. The results are shown in Table 3.

  As is clear from the results of Table 2 and Table 3, the cured product according to Example 1 maintains the same developability and adhesion as Comparative Examples 1 to 4, and further exhibits high transmittance and pattern linearity. The cured product can be formed. In addition, the coating film shrinkage rate can be reduced and the tackiness of the coating film surface can be improved. 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 is a cyclic silicone resin having weather resistance, light resistance, and heat resistance, and by using a resin imparted with photocurability and alkali developability, weather resistance, light resistance, heat resistance Can be formed. 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 (3)

(I) a photosensitive alkali-soluble resin represented by the following general formula (1) and having a carboxyl group 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 inside. X is a substituent represented by the general formula (2), and X ₁ and X ₂ each contain a polymerizable double bond, and at least one of them contains a carboxyl group. n represents the number of 3-6. ]

A photosensitive resin composition comprising (ii) a photopolymerizable monomer having at least one ethylenically unsaturated bond, and (iii) a photopolymerization initiator as essential components. The photosensitive resin composition according to claim 1, wherein X in the general formula (1) is a monovalent substituent represented by the following general 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 carbon. 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) or a hydrogen atom.

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