JP5698072B2 - Epoxy compound and polymerizable composition containing the same - Google Patents

Description

The present invention relates to a novel epoxy compound having a benzo or naphthocycloalkane skeleton having a substituent, and a polymerizable composition containing the epoxy compound.
Furthermore, the present invention provides a specific compound obtained by adding an ethylenically unsaturated bond to the epoxy compound, an alkali-developable resin composition containing a compound obtained by an esterification reaction between the compound and a polybasic acid anhydride, and The present invention relates to an alkali developable photosensitive resin composition comprising a photopolymerization initiator contained in the alkali developable resin composition.

  Conventionally, epoxy resins (compounds) have been actively developed in the fields of electronic materials and optical materials due to the excellent electrical properties, heat resistance, adhesiveness, etc. of the cured resin combined with a curing agent. For example, in the field of electronic materials, it is used for applications such as semiconductor encapsulants, and in the field of optical materials, it is used for optical devices such as antireflection films for liquid crystal displays, protective films for color filters, optical waveguides, cameras, etc. It is used for applications such as lenses, mirrors and prisms. In particular, in optical material applications, it is required to have a high refractive index for the purpose of weight reduction. In particular, when trying to obtain a cured product having a high refractive index, the curable resin composition has a high viscosity and handling properties ( There was a problem that the operability) deteriorated. In addition, the conventional epoxy resin has a problem that the obtained cured product is easily colored and a problem that heat resistance is still insufficient. Further, in applications such as a semiconductor sealing material and a glass coating material, a material having a small linear expansion coefficient is required for the purpose of achieving high adhesion.

  On the other hand, the alkali-developable photosensitive resin composition contains an alkali-developable resin containing a compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this alkali-developable photosensitive resin composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, it is used in photo-curable inks, photosensitive printing plates, printed wiring plates, various photoresists, and the like. Yes. In recent years, with the progress of miniaturization and high functionality of electronic devices, an alkali-developable photosensitive resin composition capable of forming a fine pattern with high accuracy is desired.

  Patent Documents 1 to 3 disclose a polymerizable compound having a benzo or naphthocycloalkane skeleton, and Patent Document 1 discloses an alkali developable resin using an epoxy compound as a raw material.

International Publication No. 2008/139924 JP 2009-242783 A JP 2010-120902 A

An object of the present invention is to provide an epoxy compound excellent in heat resistance and handling properties, and an epoxy compound from which a cured product with low linear expansion can be obtained, and to provide a polymerizable composition containing such an epoxy compound. is there.
A further object of the present invention is to provide an alkali-developable photosensitive resin composition that is excellent in sensitivity and adhesion, and that can obtain an appropriate pattern shape and fine pattern.

  As a result of intensive studies, the present inventor has found that a novel polymerizable compound having a benzo or naphthocycloalkane skeleton having a substituent can achieve the above object.

  This invention is made | formed based on the said knowledge, and provides the epoxy compound characterized by being represented with the following general formula (I).

（式中、Ｘは、ハロゲン原子で置換されていてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されていてもよい炭素原子数２〜２０の複素環基又はハロゲン原子を表し、Ｙはハロゲン原子で置換されていてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数７〜２０のアリールアルキル基又はハロゲン原子を表し、Ｚ ¹ 及びＺ ² はそれぞれ独立に、ハロゲン原子で置換されていてもよい炭素原子数１〜１０のアルキル基又はハロゲン原子を表し、
該アルキル基、アリール基、アリールアルキル基中のメチレン基は、互いに隣り合わない条件で、不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、Ｘは、Ｘ同士で環を形成していてもよく、
Ｌ¹は、１，２−エタンジイル基又は１，２−プロパンジイル基であり、ｎは１〜５の数を表し、ｎが２以上の場合、［Ｌ¹Ｏ］_nで表されるユニットは、エチレンオキシ基とプロピレンオキシ基のランダム共重合体又はブロック共重合体でもよく、
ｋは０〜４の数を表し、ｐは１又は２の数を表し、ｒ及びｓは、それぞれ独立に、０又は１の数を表し、ｋ又はｐが２以上の時、複数あるＸ又はＹは、同一でも異なっていてもよく、ｘは２であり、ｙは０である。）

(Wherein, X is C androgenic optionally substituted alkyl group having 1 to 10 carbon atoms in the atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, substituted with a halogen atom An arylalkyl group having 7 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom , Y being substituted with a halogen atom; An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom Or a halogen atom , Z ¹ and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or a halogen atom;
The methylene group in the alkyl group, aryl group, and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, under the condition that they are not adjacent to each other, and X is a ring of X together. May be formed,
L ¹ is a 1,2-ethanediyl group or a 1,2-propanediyl group, n represents a number of 1 to 5 , and when n is 2 or more, a unit represented by [L ¹ O] _n is , A random copolymer or block copolymer of an ethyleneoxy group and a propyleneoxy group may be used,
k represents a number of 0 to 4, p represents a number of 1 or 2 , r and s each independently represent a number of 0 or 1 , and when k or p is 2 or more, a plurality of X or Y may be the same or different, x is 2, y is Ru 0 der. )

  Moreover, this invention provides the polymeric composition characterized by containing the said epoxy compound.

  Moreover, this invention provides the epoxy addition compound characterized by having the structure which added (B) unsaturated monobasic acid to the said epoxy compound (A).

  The present invention also includes (X) a photopolymerizable unsaturated compound having a structure which is a reaction product obtained by esterification reaction of (W) the above epoxy addition compound and (C) polybasic acid anhydride. The present invention provides an alkali-developable resin composition.

  Moreover, this invention contains the (Y) photopolymerizable unsaturated compound which has a structure which is a reaction product obtained by further adding (D) an epoxy compound to the said (X) photopolymerizable unsaturated compound. An alkali-developable resin composition is provided.

  In addition, the present invention provides (Z) a photopolymerizable unsaturated compound having a structure which is a reaction product obtained by further esterifying (E) a polybasic acid anhydride with the above (Y) photopolymerizable unsaturated compound. The present invention provides an alkali-developable resin composition containing a saturated compound.

The epoxy compound and the polymerizable composition of the present invention are excellent in heat resistance and handling properties, and the cured product obtained from the polymerizable composition of the present invention exhibits a low linear expansion coefficient and a high refractive index.
The epoxy compound of the present invention is also useful as a raw material for an alkali developable resin composition, and a photopolymerization initiator is added to the alkali developable resin composition of the present invention prepared using the epoxy compound of the present invention. The alkali-developable photosensitive resin composition obtained is excellent in sensitivity, resolution, and adhesion.

  Hereinafter, the epoxy compound, polymerizable composition, epoxy addition compound, alkali-developable resin composition, and alkali-developable photosensitive resin composition of the present invention will be described in detail based on preferred embodiments.

In the above general formula (1) representing the epoxy compound of the present invention, examples of the alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom represented by X, Y, Z ¹ and Z ² include, for example, , Methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, t-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2 -Ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetra Fluoropropyl, trifluoropropyl, Perfluorobutyl, methoxy, methoxyethoxy, methoxyethoxyethoxy, methylthio, ethoxy, vinyloxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, t-butoxycarbonylmethoxy, pentyloxy, isopentyloxy, t-pentyloxy, Directly such as neopentyloxy, hexyloxy, cyclohexyloxy, isohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. Examples include chain, branched, and cyclic alkyl groups.

In the general formula (1), examples of the aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom represented by X, Y, Z ¹ and Z ² include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 1-phenanthryl, o-tolyl, m-tolyl, p-tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethyl Tylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t-butylphenyl, 2,5-di-t-butyl Phenyl, 2,6-di-t-butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4 -Chlorophenyl, 3,4-dichlorophenyl, 4-trichlorophenyl, 4-trifluorophenyl, perfluorophenyl, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2, 4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-di Tylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4 6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy , Pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecyl Phenoxy, 1-naphthoxy, 2-naphthoxy 1-anthryloxy, 1-phenanthryloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluorenyloxy, 1-tetrahydronaphthoxy, 2-tetrahydronaphthoxy, 1-acenaphthenyloxy , 1-indanyloxy, 2-indanyloxy and the like.

In the general formula (1), examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom represented by X, Y, Z ^{1 or} Z ² include benzyl, phenethyl, 2 -Phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl, benzyloxy group, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1-anthrylmethoxy and the like.

In the general formula (1), examples of the heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom represented by X, Y, Z ¹ and Z ² include pyrrolyl, pyridyl, pyrimidyl, Pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl , Isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4 -Dioxyoxazolidin-3-yl etc. are mentioned.

In the general formula (1), examples of the halogen atom represented by X, Y, Z ¹ and Z ² include fluorine, chlorine, bromine and iodine.
In the epoxy compound of the present invention, in the general formula (1), the methylene groups in the alkyl group, aryl group and arylalkyl group represented by X, Y, Z ¹ and Z ² are not adjacent to each other. And may be interrupted by an unsaturated bond, -O- or -S-. The interruption position of -O- or -S- is optional, and -O- or -S- may be directly bonded to each ring.
In addition, examples of the halogen atom that the alkyl group, aryl group, arylalkyl group, and heterocyclic group may have include fluorine, chlorine, bromine, and iodine, and the substitution position of the halogen atom is arbitrary.

  In the general formula (1), examples of the ring structure that may be formed by X include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, and lactam ring. Examples thereof include 5- to 7-membered alicyclic rings, aromatic rings and heterocyclic rings, and condensed rings such as naphthalene ring, anthracene ring, fluorene ring, acenaphthene ring, indane ring and tetralin ring.

  In the epoxy compound of the present invention, in the general formula (1), a compound in which x is 2 and y is 0 is preferable because of excellent photocurability, and among them, a compound represented by the following general formula (2) Is more preferable because it is advantageous in terms of manufacturing.

（式中、Ｘ、Ｙ、Ｚ¹、Ｚ²、Ｌ¹、ｎ、ｋ、ｒ及びｓは、上記一般式（１）と同じである。）

(In the formula, X, Y, Z ¹ , Z ² , L ¹ , n, k, r and s are the same as those in the general formula (1).)

  Furthermore, in the general formula (1) or (2), a compound in which Y is a phenyl group is preferable because it gives a polymer having a high refractive index. In the above general formula (1) or (2), a compound in which k is 0 or 1, in particular, k is 1 and X is an alkyl group having 1 to 10 carbon atoms or an aryl having 6 to 20 carbon atoms. The compound which is a group is preferable because it is more advantageous in terms of production. Moreover, in order to show the effect of the present invention more reliably, in the general formula (1) or (2), n is preferably 1 to 5, and r and s are each independently 0 to 1. Preferably there is.

As an epoxy compound of this invention represented by the said General formula (1), following compound No. 1-No. 31, but is not limited to these compounds. In the following chemical formula, L ¹ is a 1,2-ethanediyl group or a 1,2-propanediyl group, and n represents a number from 1 to 20.

The epoxy compound of the present invention can be produced by applying a conventionally known reaction, and is not particularly limited by the production method. For example, as shown in the following reaction formula 1, a bisphenol derivative (11) And the epichlorohydrin can be reacted in the presence of an alkali, a Lewis acid or a phase transfer catalyst to produce the epoxy compound of the present invention. The reaction temperature is preferably in the range of 20 to 100 ° C., particularly 30 to 80 ° C. If it is less than 20 ° C., the reaction becomes slow and a long reaction is required, and if it exceeds 100 ° C., there are many side reactions. It happens and is not preferred In the following formula, X, Y, Z ¹ , Z ² , L ¹ , k, p, r, s, x, y and n are the same as those in the general formula (1).

  Examples of the alkali used in the above reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like, and examples of the Lewis acid include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, and p-toluene. Sulfonic acids such as sulfonic acid, hydroxymethylsulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, trifluoromethanesulfonic acid, sulfosalicylic acid, sulfophthalic acid; sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid , Hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, silicotungstic acid, phosphotungstic acid and other heteropolyacids, strongly acidic ion exchange resins, activated clay, boron trifluoride, anhydrous aluminum chloride , Zinc chloride, tin tetrachloride, three Examples thereof include boron fluoride, titanium tetrachloride, activated clay, aluminum chloride, magnesium chloride, potassium permanganate, potassium chromate, and the like. Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrichloride. Octylammonium chloride, methyltridecylammonium chloride, benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidinium bromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide, N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N -A Ru-N-methylmorpholinium bromide, N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N -Ethylpiperidinium acetate, N-methyl-N-ethylpiperidinium iodide and the like.

  Moreover, a conventionally well-known solvent can be used for the said reaction, For example, Terpene, such as aromatic hydrocarbon solvents, such as toluene, xylene, cumene; terpine oil, D-limonene, pinene, etc. Hydrocarbon oils; mineral spirits, paraffinic solvents such as Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); alcoholic solvents such as methanol and ethanol; esters such as ethyl acetate Solvents: Halogen solvents such as dichloroethane, carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, chlorobenzene; cyclic ether solvents such as tetrahydrofuran and dioxane; ethers, cellosolve solvents, ketone solvents, aniline, triethylamine, pyridine, dioxane , Acetic acid, acetonitrile Carbon disulfide, and the like. Excess epichlorohydrin can also be used as a solvent.

  The amount of epichlorohydrin used in the above reaction is preferably at least 1 mole, particularly 2 to 10 moles per mole of the hydroxyl group of the bisphenol derivative (11). The amount of alkali used is that of the bisphenol derivative (11). The ratio of 0.1 to 2.0 mol, particularly 0.3 to 1.5 mol is preferable with respect to 1 mol of the hydroxyl group, and the amount of Lewis acid or phase transfer catalyst used is relative to the amount of hydroxyl group of the bisphenol derivative (11). A proportion of 0.01 to 10 mol%, particularly 0.2 to 5 mol% is preferred.

  The epoxy compound of the present invention can be used as a main component of a polymerizable composition, or can be used as an epoxy adduct added with an unsaturated monobasic acid and as a raw material for an alkali-developable resin composition.

Below, the polymeric composition of this invention using the epoxy compound of this invention is demonstrated.
The polymerizable composition of the present invention is characterized by containing the epoxy compound of the present invention represented by the general formula (1). In the polymerizable composition of the present invention, the epoxy compound of the present invention is usually blended together with a curing agent for polymerizing the epoxy compound of the present invention. The kind of the curing agent is not particularly limited, and examples thereof include polyalkylpolyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; 1,2-diaminocyclohexane, 1,4-diamino-3,6-diethylcyclohexane, Examples include alicyclic polyamines such as isophoronediamine; polyamines such as aromatic polyamines such as m-xylylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. In addition, these polyamines and glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, or various epoxy resins such as glycidyl esters of carboxylic acid are used in a conventional manner. Polyepoxy addition-modified products produced by reacting them with these; amidation-modified products produced by reacting these polyamines with carboxylic acids such as phthalic acid, isophthalic acid, and dimer acid; The conventional polyamines are reacted with aldehydes such as formaldehyde and phenols having at least one aldehyde-reactive site in the nucleus such as phenol, cresol, xylenol, t-butylphenol, and resorcin. Mannich modifications thereof are prepared by; dicyandiamide, acid anhydride, latent curing agent such as imidazoles such as 2-ethyl-4-methylimidazole; energy beam sensitive cationic polymerization initiator, and the like.

  The energy beam sensitive cationic polymerization initiator is a compound capable of releasing a substance that initiates cationic polymerization by energy beam sensitive irradiation, more specifically, energy beam irradiation as described later.

Particularly preferable examples of the energy ray-sensitive cationic polymerization initiator include compounds such as a double salt which is an onium salt that releases a Lewis acid by energy ray-sensitive irradiation, or a derivative thereof. A typical example of such a compound is a salt of a cation and an anion represented by the general formula [A] ^{v +} [B] ^v- .

The cation [A] ^{v +} is preferably onium, and its structure can be represented by, for example, [(R) _w Q] ^{v +} . R has 1 to 60 carbon atoms, represents an organic group that may contain any number of atoms other than carbon atoms, and w represents an integer of 1 to 5. The w Rs are independent and may be the same or different. Moreover, it is preferable that at least one of w R is an aromatic group. Q represents an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{v +} is z, it is necessary that the relationship v = w−z holds.

Further, the anion [B] ^v− is preferably a halide complex, and the structure thereof can be represented by, for example, [LX _u ] ^v− . L represents a metal or metalloid which is a central atom of a halide complex, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Examples thereof include Cr, Mn, and Co. X represents a halogen atom, and u represents an integer of 3 to 7. Further, when the valence of L in the anion [B] ^v− is t, it is necessary that the relationship v = ut is established.

Specific examples of the anion [LX _u ] ^v− constituting the onium salt represented by the above general formula include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF _6). ^-), hexafluoroarsenate (AsF ₆ ^-), hexachloroantimonate (SbCl ₆ ^-) and the like, preferably hexafluoroantimonate (SbF ₆ ^- is).

Further, as the anion [B] ^v− , one having a structure represented by [LX _u ⁻¹ (OH)] ^v− can also be used. L, X, and u are the same as described above. Other anions that can be used include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), and toluenesulfonate anion. And trinitrobenzenesulfonic acid anion.

Further, tetrakis (pentafluorophenyl) borate can also be used as the anion [B] ^v− .

  In the present invention, it is particularly effective to use an aromatic onium salt among such onium salts. Of these, aromatic halonium salts described in JP-A-50-151997, JP-A-50-158680, JP-A-50-151997, JP-A-52-30899, JP-A-56- No. 55420, JP-A No. 55-125105, etc., Group VIA aromatic onium salts, JP-A No. 50-158698, Group VA aromatic onium salts, JP-A No. 56-8428, Oxosulfoxonium salts described in JP-A-56-149402, JP-A-57-192429, etc., aromatic diazonium salts described in JP-A-49-17040, US Pat. No. 4,139,655 The thiopyrylium salt described in 1 is preferable.

  Particularly preferred among these aromatic onium salts are compounds having a sulfonium cation represented by the following general formula (III), (IV) or (V); compounds having a (triccumyl) iodonium cation; bis (Tertiarybutylphenyl) a compound having an iodonium cation; a compound having a triphenylsulfonium cation, and the like.

（式中、Ｒ１〜Ｒ１４は各々同一でも異なっていてもよい水素原子、ハロゲン原子、酸素原子若しくはハロゲン原子を含んでもよい炭化水素基、又は置換基がついてもよいアルコキシ基であり、Ａｒは１以上の水素原子が置換されていてもよいフェニル基である。）

(In the formula, R1 to R14 are each a hydrogen atom, a halogen atom, an oxygen atom or a hydrocarbon group which may contain a halogen atom, which may be the same or different, or an alkoxy group which may have a substituent; The above hydrogen atom is a phenyl group which may be substituted.)

  Preferred examples of the aromatic onium salt include 4- (4-benzoyl-phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate; 4,4′-bis [bis ((β-hydroxyethoxy) Phenyl) sulfonio] phenyl sulfide-bis-hexafluorophosphate, 4,4′-bis [bis ((β-hydroxyethoxy) phenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate; 4,4′-bis [bis (Fluorophenyl) sulfonio] phenyl sulfide-bis-hexafluorophosphate, 4,4′-bis [bis (fluorophenyl) sulfonio] phenyl sulfide-bis-hexafluoroantimonate; 4,4′-bis (diphenylsulfonio) Phenyls Rufido-bis-hexafluorophosphate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate; 4- (4-benzoylphenylthio) phenyl-di- (4- (β-hydroxyethoxy ) Phenyl) sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate; 4- (4-benzoylphenylthio) phenyl-di -(4-Fluorophenyl) sulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate; 4- (4-benzoylphenylthio) phenyl -Diphenylsulfonium hexafluorophosphate, 4- (4-benzoylphenylthio) phenyl-diphenylsulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluorophosphate, 4- (phenylthio) phenyl-di- (4- (β-hydroxyethoxy) phenyl) sulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (phenylthio ) Phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate; 4- (phenylthio) phenyl-diphenylsulfonium hexafluorophosphate, 4- (fluoro Phenylthio) phenyl-diphenylsulfonium hexafluoroantimonate; 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) Phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate; 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyldiphenylsulfonium Hexafluoroantimonate; 4- (2-chloro-4-benzoylphenylthio) phenylbis (4-hydroxyphenyl) sulfonium hexafluorophosphate, 4- (2-c (Ro-4-benzoylphenylthio) phenyl bis (4-hydroxyphenyl) sulfonium hexafluoroantimonate; triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate; (tolylcumyl) iodonium hexafluorophosphate, (tolylcumyl) iodonium hexa Fluoroantimonate, (tolylcumyl) iodonium tetrakis (pentafluorophenyl) borate; bis (tertiarybutylphenyl) iodonium hexafluorophosphate, bis (tertiarybutylphenyl) iodonium hexafluoroantimonate, bis (tertiarybutylphenyl) iodonium tetrakis (Pentafluorophenyl) borate; benzyl-4-hydroxy Phenylmethylsulfonium hexafluorophosphate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; benzyldimethylsulfonium hexafluorophosphate, benzyldimethylsulfonium hexafluoroantimonate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; 4-acetoxyphenyldimethylsulfonium hexafluorophosphate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate; 4-methoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4 -Methoxyca Rubonyloxyphenyldimethylsulfonium hexafluoroantimonate; 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluorophosphate, 4-ethoxycarbonyloxyphenyldimethylsulfonium hexafluoroantimonate; α-naphthylmethyldimethylsulfonium hexafluorophosphate, α-naphthylmethyldimethyl Α-naphthylmethyltetrahydrothiophenium hexafluorophosphate, α-naphthylmethyltetrahydrothiophenium hexafluoroantimonate; cinnamyldimethylsulfonium hexafluorophosphate, cinnamyldimethylsulfonium hexafluoroantimonate; cinnamyl Tetrahydrothiooff Ni-hexafluorophosphate, cinnamyltetrahydrothiophenium hexafluoroantimonate; N- (α-phenylbenzyl) cyanopyridinium hexafluorophosphate, N- (α-phenylbenzyl) -2-cyanopyridinium hexafluoroantimonate; N -Cinnamyl-2-cyanopyridinium hexafluorophosphate, N-cinnamyl-2-cyanopyridinium hexafluoroantimonate; N- (α-naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, N- (α-naphthylmethyl)- 2-cyanopyridinium hexafluoroantimonate; N-benzyl-2-cyanopyridinium hexafluorophosphate, N-benzyl-2-cyanopyridinium hexafluoroanti Sulfonate; (4-benzoyl) phenyl bis (4-fluorophenyl) sulfonium tetrakis (3,5-difluoro-4-methoxyphenyl) borate, and the like.

  Other preferable energy ray-sensitive cationic polymerization initiators include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl. Examples thereof include iron / allene complexes such as iron (II) -tris (trifluoromethylsulfonyl) methanide, aluminum complexes / photolytic silicon compound-based initiators, and the like.

  In the polymerizable composition of the present invention, when a curing agent other than the energy ray-sensitive cationic polymerization initiator is used, the content thereof is preferably 1 to 500 parts by mass, more preferably 100 parts by mass of the epoxy compound of the present invention. Is 10 to 200 parts by mass, and when an energy ray-sensitive cationic polymerization initiator is used as a curing agent, the preferred amount used is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the epoxy compound of the present invention. More preferably, it is 0.5-15 mass parts.

  Further, the polymerizable composition of the present invention includes a curing catalyst, a reactive and / or non-reactive diluent (plasticizer), a filler, a pigment, a silane coupling agent, a surfactant, if necessary. Lubricants, thickeners, thixotropic agents, antioxidants, photosensitizers, light stabilizers, UV absorbers, flame retardants, antifoaming agents, rust inhibitors, storage stabilizers, colloidal silica, colloidal alumina, etc. Conventional additives may be contained, and resins may be used in combination. In the polymerizable composition of the present invention, these optional additives are preferably 500 parts by mass or less in total with respect to 100 parts by mass of the epoxy compound of the present invention.

  A solvent may be used in the polymerizable composition of the present invention. In this case, the amount of the solvent used is such that the total content of the epoxy compound and the curing agent of the present invention is preferably 5 to 90% by mass, more preferably 10 to 50% by mass in the polymerizable composition of the present invention. It is better to be in the range. Specific examples of the solvent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1 Ether solvents such as 1,2-diethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, and n-butyl acetate; ethylene glycol monomethyl ether, ethylene glycol Cellosolve solvents such as monoethyl ether, propylene glycol monomethyl ether acetate; methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyla Alcohol solvents such as coal; BTX solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; Paraffinic solvents such as Mineral Spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride Solvent: Halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N-methylpyrrolidone, etc. , Ketones or cellosolve solvents It is preferred. Moreover, you may make it contain in the polymeric composition of this invention as it is, without removing the solvent used when synthesize | combining the epoxy compound of this invention.

  The polymerizable composition of the present invention can be cured by a conventional method according to the type of the curing agent used. When an energy ray-sensitive cationic polymerization initiator is used as the curing agent, curing is performed by irradiating energy rays. The energy ray may be any as long as it induces the decomposition of the cationic polymerization initiator, but is preferably an ultra-high, high, medium, low-pressure mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten Lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, etc. High energy rays such as electromagnetic energy having an angstrom wavelength, electron beam, X-ray, radiation, etc. are used.

  The cured product of the polymerizable composition of the present invention is useful for optical parts such as an optical lens, an optical film, a light guide plate, a waveguide, an optical element, and an optical connector. The shape of the cured product of the polymerizable composition of the present invention is not particularly limited, and may be an appropriate shape such as a lens shape, a film shape, a prism shape, or a plate shape depending on the application. Furthermore, the material may be coated or sealed by curing on other materials.

  The polymerizable composition of the present invention can be used as an ink, a protective film, a paint, a coating agent, an adhesive, an insulating material, a structural material, an optical disk, a sealing agent, an optical modeling agent, and the like, in addition to the above optical component. .

Next, the epoxy addition compound of this invention is demonstrated.
The epoxy addition compound of the present invention has a structure in which (B) an unsaturated monobasic acid is added to the epoxy compound of the present invention (A). The epoxy adduct of the present invention is useful as a raw material for a photosensitive composition for coating, as well as being used as a raw material for an alkali-developable resin composition and an alkali-developable photosensitive resin composition of the present invention described later.

  (A) When (B) an unsaturated monobasic acid is added to the epoxy compound of the present invention, (A) one epoxy group of the epoxy compound of the present invention is (B) a carboxyl of an unsaturated monobasic acid. The group is preferably added at a ratio of 0.1 to 1.0, more preferably 0.3 to 1.0.

  (B) Unsaturated monobasic acid is used to improve the sensitivity of the alkali-developable resin composition. For example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxy Examples thereof include ethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclopentadiene / malate or polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups. It is done.

  The polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups includes, for example, one hydroxyl group and two or more (meth) acryloyl groups in one molecule. It can be obtained by reacting the polyfunctional (meth) acrylate with dibasic acid anhydride or carboxylic acid.

  Examples of the polyfunctional (meth) acrylate having one carboxyl group and two or more (meth) acryloyl groups include compounds represented by the following [Chemical Formula 12] to [Chemical Formula 14].

The epoxy adduct of the present invention can be used as a raw material for an alkali-developable resin composition. The alkali-developable resin composition of the present invention contains any one or more of the following components (X), (Y) and (Z). By appropriately using the following components (X), (Y), and (Z), it becomes easy to adjust the acid value of the alkali-developable resin composition, so that it can be adjusted to a preferable development time.
(X) Component: (W) Photopolymerizable unsaturated compound having a structure which is a reaction product obtained by esterification reaction of the epoxy adduct of the present invention and (C) polybasic acid anhydride (Y) : Photopolymerizable unsaturated compound having a structure which is a reaction product obtained by further adding (D) an epoxy compound to the photopolymerizable unsaturated compound as component (X) (Z) Component: (Y) The photopolymerizable unsaturated compound having a structure which is a reaction product obtained by further esterifying (E) a polybasic acid anhydride with the photopolymerizable unsaturated compound as a component

(W) In the esterification reaction of the epoxy adduct of the present invention and (C) polybasic acid anhydride, (W) the acid of (C) polybasic acid anhydride for one hydroxyl group of the epoxy adduct of the present invention The reaction is carried out so that the ratio of the anhydride structure is preferably 0.1 to 1.0, more preferably 0.3 to 0.95.
When (D) an epoxy compound is further added to the photopolymerizable unsaturated compound as component (X), (W) used for the preparation of component (X) 1 hydroxyl group of the epoxy adduct of the present invention (D) It is made to add so that the ratio of the epoxy group of an epoxy compound may become 0.1-1.0 piece, More preferably, it is 0.3-0.9 piece.
When the (E) polybasic acid anhydride is further esterified with the photopolymerizable unsaturated compound as the component (Y), (W) the epoxy addition of the present invention used for the preparation of the component (X) The ratio of the acid anhydride structure of the (E) polybasic acid anhydride to one hydroxyl group of the product is preferably 0.1 to 1.0, more preferably 0.3 to 0.7. Let

  Examples of the (C) polybasic acid anhydride used for obtaining the alkali-developable resin composition of the present invention include succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, phthalic acid anhydride, Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic acid anhydride, methyl nadic acid anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride Adducts, monoanhydrides such as dodecenyl succinic anhydride, methyl hymic acid anhydride, methyl hexahydrophthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenyltetrasulfonic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,5-trical Xycyclopentyl acetic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, 2,2′-3,3′-benzophenone tetracarboxylic anhydride, 5- ( 2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,3′-4,4′-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydrotri Examples include meridates, dianhydrides such as meso-butane-1,2,3,4-tetracarboxylic acid anhydride, and dianhydrides such as glycerol tris anhydro trimellitate, and among these, dianhydrides Or the combination of a diacid anhydride and a monoacid anhydride is preferable.

Examples of the (D) epoxy compound used for the preparation of the alkali-developable resin composition of the present invention include a monofunctional epoxy compound or a polyfunctional epoxy compound such as the epoxy compound of the present invention.
The monofunctional epoxy compound is used to adjust the acid value of the alkali-developable resin composition. For example, glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether ether, pentyl glycidyl ether , Hexyl glycidyl ether, heptyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, propargyl glyci Ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl ether, p -Cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinylcyclohexane, styrene Oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, represented by the following [Chemical Formula 15] to [Chemical Formula 18] Compounds, and the like.

The polyfunctional epoxy compound is used to adjust the development speed by increasing the molecular weight of the photopolymerizable unsaturated compound. In addition to the epoxy compound of the present invention, for example, a bisphenol type epoxy compound and glycidyl ethers are used. be able to.
As the bisphenol type epoxy compound, an alkylidene bisphenol polyglycidyl ether type epoxy resin and a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,8-octanediol diglycidyl ether. 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol di Glycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1 Tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, include 1,1,1,1- tetra (glycidyloxymethyl) methane.

  Other polyfunctional epoxy compounds include other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, and dicyclopentadiene novolac epoxy compounds; , 4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 1-epoxyethyl -Cycloaliphatic epoxy compounds such as 3,4-epoxycyclohexane; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester, etc. Glycidyl esters such as tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol and N, N-diglycidylaniline; complex such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate Cyclic epoxy compounds; Dioxide compounds such as dicyclopentadiene dioxide; naphthalene type epoxy compounds, triphenylmethane type epoxy compounds, dicyclopentadiene type epoxy compounds, and the like can be used.

As the (E) polybasic acid anhydride used as necessary to obtain the alkali-developable resin composition of the present invention, those mentioned as the (C) polybasic acid anhydride can be used.
Moreover, each component of (A)-(E) can be used by 1 type or in mixture of 2 or more types.

  The photopolymerizable unsaturated compound of component (Z) may be further added with (D) an epoxy compound, followed by further esterification of (E) polybasic acid anhydride, or these may be repeated. . In addition, (D) an epoxy compound is added to a photopolymerizable unsaturated compound having a structure obtained by reacting each component of (A) to (E), and then replaced with (E) a polybasic acid anhydride. The lactone compound may be esterified.

The photopolymerizable unsaturated compound as the components (X), (Y), and (Z) preferably has a weight average molecular weight Mw of 1000 to 20000 and a number average molecular weight Mn of 900 to 100,000.
In the alkali-developable resin composition of the present invention, the content of the component (X), (Y) or (Z) having a structure obtained by reacting the components (A) to (E) is preferably It is 1-70 mass%, More preferably, it is 3-30 mass%. In the alkali-developable resin composition of the present invention, the acid value of the solid content (that is, the photopolymerizable unsaturated compound) is preferably 20 to 100 mg · KOH / g, more preferably 50 to 100 mg · KOH / g. is there.

  The alkali-developable resin composition of the present invention may contain a solvent in addition to the photopolymerizable unsaturated compound. For example, when the content of the photopolymerizable unsaturated compound is within the above preferred range A solvent can be used for the remainder other than the photopolymerizable unsaturated compound. Specific examples of the solvent include those exemplified as the solvent used in the alkali-developable photosensitive resin composition described later. Moreover, you may make it contain in the alkali developable resin composition of this invention as it is, without removing the solvent used when synthesize | combining the said photopolymerizable unsaturated compound from (A)-(E) component.

  The alkali-developable resin composition of the present invention is mainly used as an alkali-developable photosensitive resin composition by being mixed with (F) a photopolymerization initiator and, if necessary, a solvent. Below, the said alkali-developable photosensitive resin composition (henceforth the alkali-developable photosensitive resin composition of this invention) is demonstrated based on preferable embodiment.

The alkali-developable photosensitive resin composition of the present invention comprises (F) a photopolymerization initiator in at least the alkali-developable resin composition of the present invention containing the photopolymerizable unsaturated compound. .
In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerizable unsaturated compound is preferably a proportion of the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition, preferably 50. It is -90 mass%, More preferably, it is 60-80 mass%.

  As the photopolymerization initiator (F), conventionally known compounds can be used. For example, benzoyl peroxide, 2,2′-azobisisobutyronitrile, benzophenone, phenyl biphenyl ketone, 1-hydroxy -1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholy-2- (4′-methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy- -(4'-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6- Bis (2′-morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (Trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -s-triazine, 2- (p-butoxy Styryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, bis ( 2,4,6-trimethylbenzoyl) -phenylphosphine oxide, as well as JP 2000-80068, JP 2001-233842, JP 2005-97141, JP 2006-516246, JP 3860170. And the compounds described in Japanese Patent No. 3,798,008 and International Publication No. 2006/019873. Among these, the compound represented by the following general formula (a) or (c) is preferable.

（式中、Ｒ⁷¹、Ｒ⁷²及びＲ⁷³は、それぞれ独立して、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ及びＲ’は、それぞれ独立して、アルキル基、アリール基、アリールアルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアリールアルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合又はエステル結合により中断されていてもよく、また、Ｒ及びＲ’は一緒になって環を形成していてもよく、Ｒ⁷⁴は、ハロゲン原子又はアルキル基を表し、Ｒ⁷⁵は、水素原子、ハロゲン原子、アルキル基又は下記一般式（ｂ）で表される置換基を表し、ｇは０〜４の整数であり、ｇが２以上の時、複数のＲ⁷⁴は異なる基でもよい。）

(Wherein R ⁷¹ , R ⁷² and R ⁷³ each independently represent R, OR, COR, SR, CONRR ′ or CN, and R and R ′ each independently represent an alkyl group or an aryl group) Represents an arylalkyl group or a heterocyclic group, which may be substituted with a halogen atom and / or a heterocyclic group, and among these, the alkylene part of the alkyl group and the arylalkyl group is an unsaturated bond, an ether bond, R may be interrupted by a thioether bond or an ester bond, R and R ′ may be combined to form a ring, R ⁷⁴ represents a halogen atom or an alkyl group, and R ⁷⁵ is hydrogen. An atom, a halogen atom, an alkyl group or a substituent represented by the following general formula (b) is represented, g is an integer of 0 to 4, and when g is 2 or more, a plurality of R ⁷⁴ may be different groups. )

（式中、環Ｍはシクロアルカン環、芳香環又は複素環を表し、Ｒ⁷⁶はハロゲン原子又はアルキル基を表し、Ｙ⁷¹は酸素原子、硫黄原子又はセレン原子を表し、Ｚ⁷¹は炭素原子数１〜５のアルキレン基を表し、ｈは０〜４の整数であり、ｈが２以上の時、複数のＲ⁷⁶は異なる基でもよい。）

(In the formula, ring M represents a cycloalkane ring, an aromatic ring or a heterocyclic ring, R ⁷⁶ represents a halogen atom or an alkyl group, Y ⁷¹ represents an oxygen atom, a sulfur atom or a selenium atom, and Z ⁷¹ represents the number of carbon atoms. Represents an alkylene group of 1 to 5, h is an integer of 0 to 4, and when h is 2 or more, a plurality of R ⁷⁶ may be different groups.)

（式中、Ｒ1及びＲ2は、それぞれ独立して、Ｒ¹¹、ＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＣＯＮＲ¹²Ｒ¹³又はＣＮを表し、Ｒ¹¹、Ｒ¹²及びＲ¹³は、それぞれ独立して、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、アルキル基、アリール基、アリールアルキル基及び複素環基の水素原子は、更にＯＲ²¹、ＣＯＲ²¹、ＳＲ²¹、ＮＲ²²Ｒ²³、ＣＯＮＲ²²Ｒ²³、−ＮＲ²²−ＯＲ²³、−ＮＣＯＲ²²−ＯＣＯＲ²³、−Ｃ（＝Ｎ−ＯＲ²¹）−Ｒ²²、−Ｃ（＝Ｎ−ＯＣＯＲ²¹）−Ｒ²²、ＣＮ、ハロゲン原子、−ＣＲ²¹＝ＣＲ²²Ｒ²³、−ＣＯ−ＣＲ²¹＝ＣＲ²²Ｒ²³、カルボキシル基又はエポキシ基で置換されていてもよく、Ｒ²¹、Ｒ²²及びＲ²³は、それぞれ独立して、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、上記Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ²¹、Ｒ²²及びＲ²³で表される置換基のアルキレン部分のメチレン基は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合、チオエステル結合、アミド結合又はウレタン結合により１〜５回中断されていてもよく、上記置換基のアルキル部分は分岐側鎖があってもよく、環状アルキルであってもよく、上記置換基のアルキル末端は不飽和結合であってもよく、また、Ｒ¹²とＲ¹³及びＲ²²とＲ²³はそれぞれ一緒になって環を形成していてもよい。Ｒ³及びＲ⁴は、それぞれ独立して、Ｒ¹¹、ＯＲ¹¹、ＳＲ¹¹、ＣＯＲ¹¹、ＣＯＮＲ¹²Ｒ¹³、ＮＲ¹²ＣＯＲ¹¹、ＯＣＯＲ¹¹、ＣＯＯＲ¹¹、ＳＣＯＲ¹¹、ＯＣＳＲ¹¹、ＣＯＳＲ¹¹、ＣＳＯＲ¹¹、ＣＮ、ハロゲン原子又は水酸基を表し、ａ及びｂは、それぞれ独立して、０〜４である。Ｘ1は、直接結合又はＣＯを表し、Ｘ²は、酸素原子、硫黄原子、セレン原子、ＣＲ³¹Ｒ³²、ＣＯ、ＮＲ³³又はＰＲ³⁴を表し、Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴は、それぞれ独立して、Ｒ¹¹、ＯＲ¹¹、ＣＯＲ¹¹、ＳＲ¹¹、ＣＯＮＲ¹²Ｒ¹³又はＣＮを表し、Ｒ³は、−Ｘ²−を介して隣接するベンゼン環の炭素原子の１つと結合して環構造を形成していてもよく、或いはＲ³とＲ⁴が一緒になって環を形成していてもよく、Ｒ³¹、Ｒ³³及びＲ³⁴は、それぞれ独立して、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよい。）

Wherein R 1 and R 2 each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ¹¹ , R ¹² and R ¹³ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, an alkyl group, The hydrogen atoms of the aryl group, arylalkyl group and heterocyclic group are further OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , —NR ²² —OR ²³ , —NCOR ²² —OCOR ²³ , — ^{C (= N-OR 21)} -R 22, -C (= N-OCOR 21) -R 22, CN, halogen ^{atom, -CR 21 = CR 22 R 23} , -CO-CR 21 = CR 22 R 23, R ² may be substituted with a carboxyl group or an epoxy group ¹ , R ²² and R ²³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon atom. The methylene group of the alkylene part of the substituent represented by the formula 2 to 20 and represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is an unsaturated bond, an ether bond, It may be interrupted 1 to 5 times by a thioether bond, an ester bond, a thioester bond, an amide bond or a urethane bond, and the alkyl part of the substituent may have a branched side chain or a cyclic alkyl, The alkyl terminal of the substituent may be an unsaturated bond, and R ¹² and R ¹³ and R ²² and R ²³ may be combined to form a ring, and R ³ and R ⁴ are independently, R ^11, O ^{11, SR 11, COR 11,} CONR 12 R 13, NR 12 COR 11, OCOR 11, COOR 11, SCOR 11, OCSR 11, COSR 11, CSOR 11, CN, a halogen atom or a hydroxyl group, a and b, each independently 0 to 4 .X1 represents a direct bond or CO, X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ³¹ R ^32, CO, a NR ³³ or PR ^34, R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and R ³ is adjacent via —X ² —. It may be bonded to one of the carbon atoms of the benzene ring to form a ring structure, or R ³ and R ⁴ may be combined to form a ring, and R ³¹ , R ³³ and R ³⁴ Each independently with one of the adjacent benzene rings It may form a ring me. )

  In the alkali-developable photosensitive resin composition of the present invention, the content of the photopolymerization initiator (F) is preferably a ratio in the total mass of the total solid content excluding the solvent from the alkali-developable photosensitive resin composition. It is 0.1-40 mass%, More preferably, it is 1.0-10 mass%. Moreover, the said (F) photoinitiator can be used by 1 type or in mixture of 2 or more types.

The solvent contained in the alkali-developable photosensitive resin composition of the present invention is not particularly limited as long as it is a solvent that can dissolve or disperse the above-mentioned components. For example, methyl ethyl ketone, methyl amyl ketone, diethyl ketone Ketones such as acetone, methyl isopropyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; acetic acid Ester solvents such as methyl, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, acetic acid-n-butyl; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, etc. Cellsolv solvent; alcohol solvent such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; BTX solvent such as benzene, toluene, xylene; hexane, heptane, octane, cyclohexane, etc. Aliphatic hydrocarbon solvents; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.), etc. Paraffinic solvents; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, trichloroethylene, and methylene chloride; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, Acetonitrile, disulfide Element, N, N- dimethylformamide, N- methylpyrrolidone, and among these, ketones or cellosolve solvent. These solvents can be used alone or in combination of two or more.
In the alkali-developable photosensitive resin composition of the present invention, the content of the solvent is preferably 5 to 40% by mass, more preferably 15 to 30% by mass, based on the total solid content in the alkali-developable photosensitive resin composition. It is good to adjust it to be%.

  The colored alkali-developable photosensitive resin composition of the present invention is obtained by adding the color material (G) to the alkali-developable photosensitive resin composition of the present invention. (G) As a coloring material, various pigments and dyes can be used.

As the pigment used as the colorant (G) in the colored alkali-developable photosensitive resin composition of the present invention, for example, any known pigment used in the production of conventional color filters can be used. Specific examples of organic pigments are shown by color index (CI) numbers below. In the list below, “x” represents C.I. I. It is an integer that can be arbitrarily selected from the numbers.
・ PigmentBlue:
<C. I> 1, 1: 2, 1: x, 9: x, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 24, 24: x, 56, 60, 61, 62
・ PigmentGreen:
<C. I> 1,1: x, 2,2: x, 4,7,10,36
・ Pigment Orange
<C. I> 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 59, 60, 61, 62, 64
・ PigmentRed
<C. I> 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 3, 81: x, 83, 88, 90, 112, 119, 122, 123, 144, 146, 149, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 224, 226
・ PigmentViolet:
<C. I> 1, 1: x, 3, 3: 3, 3: x, 5: 1, 19, 23, 27, 32, 42
・ Pigment Yellow
<C. I> 1, 3, 12, 13, 14, 16, 17, 24, 55, 60, 65, 73, 74, 81, 83, 93, 95, 97, 98, 100, 101, 104, 106, 108, 109,110,113,114,116,117,119,120,126,127,128,129,138,139,150,151,152,153,154,156,175

  Further, as black pigments, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # manufactured by Mitsubishi Chemical Corporation 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, diamond black LI, diamond black LH, diamond black N339, diamond Rack SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LR, Can Curve Inc. Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa carbon black ColorBlackFw200, ColorBlackFw2, ColorBlackFw2V, ColorBlackFw1, ColorBlack Fw18, ColorBlackS170, ColorBlackS160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack350, PrintexU, PrintexV, Printex140U, Printex140V (both trade names).

  Other pigments include miloli blue, iron oxide, titanium oxide, calcium carbonate, magnesium carbonate, silica, alumina, cobalt, manganese, talc, chromate, ferrocyanide, various metal sulfates, sulfides, selenides, Inorganic pigments such as phosphate ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridiane, emerald green, and cobalt green can also be used. These pigments can be used alone or in combination of two or more.

  The dyes that can be used as the colorant (G) include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes. Examples thereof include dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, cyanine dyes, and the like. These may be used alone or in combination of two or more.

  In the colored alkali-developable photosensitive resin composition of the present invention, the content of the colorant (G) is preferably a ratio of the total mass of the total solid excluding the solvent from the colored alkali-developable photosensitive resin composition. It is 0.5-70 mass%, More preferably, it is 5-60 mass%.

  The alkali-developable resin composition, the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention further contain a monomer having an unsaturated bond, a chain transfer agent, a surfactant, and the like. be able to.

Examples of the monomer having an unsaturated bond include: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobutyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, stearyl acrylate, acrylic Methoxyethyl acid, dimethylaminoethyl acrylate, zinc acrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butyl methacrylate, methacrylic acid Acid-t-butyl, cyclohexyl methacrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythris Tall tetraacrylate, pentaerythritol triacrylate, tricyclodecane dimethylol diacrylate and the like. These may be used alone or in combination of two or more.
In the (colored) alkali-developable photosensitive resin composition of the present invention, the content of the monomer having an unsaturated bond is the total mass of all solids excluding the solvent from the (colored) alkali-developable photosensitive resin composition. The proportion is preferably 0.01 to 30% by mass, more preferably 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass.

  Examples of the chain transfer agent include thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3 -Mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto- 2-butanol, mercapto Enol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopro Mercapto compounds such as pionate), disulfide compounds obtained by oxidizing the mercapto compound, iodinated alkyls such as iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Compounds. These may be used alone or in combination of two or more.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these can be used alone or in combination of two or more.

  In the alkali-developable resin composition, alkali-developable photosensitive resin composition, and colored alkali-developable photosensitive resin composition of the present invention, the properties of the cured product are improved by using a thermoplastic organic polymer. You can also. Examples of the thermoplastic organic polymer include polystyrene, polymethyl methacrylate, methyl methacrylate-ethyl acrylate copolymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid- Examples include methyl methacrylate copolymer, polyvinyl butyral, cellulose ester, polyacrylamide, and saturated polyester. These may be used alone or in combination of two or more.

  The alkali-developable resin composition, the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention include anisole, hydroquinone, pyrocatechol, t-butylcatechol, Conventional additives such as a thermal polymerization inhibitor such as phenothiazine; a plasticizer; an adhesion promoter; a filler; an antifoaming agent; a dispersing agent; a leveling agent; a silane coupling agent; These may be used alone or in combination of two or more.

  The (colored) alkali-developable photosensitive resin composition of the present invention can be cured by irradiation with actinic light. When curing, the (colored) alkali-developable photosensitive resin composition of the present invention is a known means such as spin coater, bar coater, roll coater, curtain coater, various screen printing, ink jet printing, immersion, etc. It can be applied on a supporting substrate such as metal, paper or plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  The use of the (colored) alkali-developable photosensitive resin composition of the present invention is not particularly limited, and photocurable paint, photocurable adhesive, printing plate, photoresist for printed wiring board, liquid crystal display, plasma display Further, it can be used for various applications such as formation of liquid crystal division alignment control projections or color filter pixel portions used in electroluminescence panels and video cameras.

  In addition, as an active light source used for curing the alkali-developable photosensitive resin composition and the colored alkali-developable photosensitive resin composition of the present invention, a light source that emits light having a wavelength of 300 to 450 nm is used. For example, ultrahigh pressure mercury, mercury vapor arc, carbon arc, xenon arc, or the like can be used.

  EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated further in detail, this invention is not limited by these Examples.

Synthesis Example 1 Production of 1,1-bis [4- (2-glycidyloxyethoxy) phenyl] -3-phenylindane (n = 1 in compound No. 7, L ¹ = 1,2-ethanediyl group) The following epoxy compound was synthesized by the procedure described above.

  158.6 g of epichlorohydrin was added to 50.0 g of 1,1-bis [4- (2-hydroxyethoxy) phenyl] -3-phenylindane, the temperature was raised to 60 ° C., and a 50 wt% tetramethylammonium chloride aqueous solution. After adding 0.47 g, the pressure was reduced to 120 mmHg. Under reduced pressure, 26.57 g of a 48 wt% aqueous sodium hydroxide solution was added dropwise while controlling the reaction system at 60 to 65 ° C. Water produced by the aqueous sodium hydroxide solution was separated by a Dean-Stark tube. After completion of dropping, the reaction was continued for an additional 1.5 hours. Thereafter, epichlorohydrin was distilled off, and the remainder was dissolved in 124.03 g of toluene, 3.1 g of Kyoward 600S and Kyoword 700SH were added, and alkali adsorption treatment was performed at 50 to 60 ° C. for 1 hour. After filtration, the product was washed twice with 62.02 g of ion-exchanged water, and then toluene was distilled off to obtain 47.88 g of a reaction product. This was separated and purified by silica gel column chromatography (developing solvent: toluene / ethyl acetate = 4/1) to obtain 37.12 g (yield 60%) of a pale yellow transparent viscous liquid. As a result of various analyses, it was confirmed that the obtained viscous liquid was the target epoxy compound. The results are shown below.

(1) ¹ H-NMR (acetone-d ₆ ) chemical shift (ppm)
2.54 (dd: 2H), 2.70 (dd: 2H), 2.83 (t: 1H), 3.07-3.10 (m: 2H), 3.20 (dd: 1H), 3 .36-3.41 (m: 2H), 3.78-3.84 (m: 6H), 4.10-4.20 (m: 5H), 6.83-6.89 (m: 5H) , 7.08-7.35 (m: 12H)
(2) IR spectrum (cm ^-1 )
3029, 2927, 1739, 1607, 1508, 1454, 1364, 1249, 1182, 1120, 1065, 913, 830, 758, 703
(3) Epoxy equivalent (g / eq)
288.8

[Evaluation Example 1]
The decomposition temperature and melt viscosity of the epoxy compound obtained in Synthesis Example 1 and the following comparative compounds 1 and 2 were measured by the following procedures. The results are shown in Table 1.
(Decomposition temperature)
The decomposition temperature was measured at a measurement temperature of 30 to 500 ° C. and a heating rate of 10 ° C./min with a thermogravimetric / suggested thermal analyzer (EXSTAR TG / DTA6200, manufactured by SII Nano Technology).
(Melt viscosity)
Using a cone plate viscometer (R80, manufactured by Toki Sangyo Co., Ltd.), a measurement temperature of 60 ° C., a rotation speed of 20 rpm, No. The viscosity at the time of melting was measured under the condition of 7 cone plates. The viscometer was calibrated at 25 ° C. using a standard solution for JIS 160,000 calibration.

  As is apparent from the results of [Table 1], the epoxy compound obtained in Synthesis Example 1 having a phenylindane skeleton is thermally stable as compared with Comparative Compound 1 having a fluorene skeleton, and has a viscosity at a high temperature. Low and has particularly excellent characteristics in terms of handling. In addition, the epoxy compound obtained in Synthesis Example 1 has substantially the same viscosity as the comparative compound 2 having an indane skeleton having no substituent, but is very stable thermally.

[Example 1] Production of polymerizable composition 5.00 g of the epoxy compound obtained in Synthesis Example 1 and 2.62 g of methylhexahydrophthalic anhydride (MeHHPA, manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing agent were mixed. And heated to 130 ° C. to dissolve. Immediately after dissolution confirmation, the mixture was cooled to 70 ° C., and 0.05 g of 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a curing catalyst and mixed to prepare the polymerizable composition of the present invention. Obtained.
Apply the polymerizable composition of the present invention adjusted to 50 ° C. to a glass plate heated to 80 ° C. with a bar coater so that bubbles do not enter, and sandwich it with another glass plate so that the film pressure is uniform. Fixed with. Curing treatment was performed in an oven at 100 ° C. for 1 hour and at 150 ° C. for 1 hour, the glass plate was removed, and a cured product having a thickness of 400 μm was obtained. The linear expansion coefficient and softening point of the cured product were measured by the following methods. The results are shown in [Table 2].
(Linear expansion coefficient and softening point)
The cured product is cut into 3 mm × 20 mm, and the coefficient of linear expansion is measured with a thermomechanical analyzer (EXSTAR TMA / 6000, manufactured by SII Nanotechnology) under the conditions of a measurement temperature of 35 to 350 ° C. and a temperature increase rate of 10 ° C./min. And the softening point was measured.

[Comparative Example 1]
A polymerizable composition was prepared in the same manner as in Example 1 except that the epoxy compound was changed to Comparative Compound 3 below, a cured product was obtained from the polymerizable composition, and its linear expansion coefficient and softening point were measured. did. The results are shown in [Table 2].

  As is apparent from the results of [Table 2], the cured product formed from the polymerizable composition containing the epoxy compound of the present invention has a low coefficient of linear expansion, and thus has excellent adhesion to substrates such as glass. .

[Example 2-1] Alkali-developable resin composition No. Production of 1 (A) 10.0 g of the epoxy compound obtained in Synthesis Example 1 (hereinafter also referred to as compound a-1) as an epoxy compound, and (B) acrylic acid (hereinafter also referred to as compound b) as an unsaturated monobasic acid. ) 2.55 g, 2,6-di-t-butyl-p-cresol 0.035 g, tetrabutylammonium chloride 0.063 g, and propylene glycol monomethyl ether acetate (PGMAc) 8.36 g were charged at 90 ° C. for 1 hour. The mixture was stirred at 105 ° C. for 1 hour and 120 ° C. for 17 hours. (C) 2.49 g of succinic anhydride (hereinafter also referred to as compound c-1), 0.056 g of tetrabutylammonium chloride, and 3.75 g of PGMAc were added as a polybasic acid anhydride at 100 ° C. Stir for 5 hours. Further, (D) 3.60 g of compound a-1 as an epoxy compound and 0.018 g of 2,6-di-t-butyl-p-cresol were added, and after stirring at 90 ° C. for 90 minutes and 120 ° C. for 5 hours. And 9.97 g of PGMAc, and the alkali developing resin composition No. 1 as the target product as a PGMAc solution. 1 (Mw = 5920, Mn = 2720, acid value (solid content) 42 mg · KOH / g). The obtained alkali developable resin composition No. 1 contained 44.5 mass% of (Y) photopolymerizable unsaturated compound which is a reaction product.
In addition, alkali developable resin composition No. (Y) The photopolymerizable unsaturated compound contained in 1 has a structure in which compound (b) as component (B) is added to compound a-1 as component (A) (W) hydroxyl group 1 of epoxy adduct It was obtained by reacting the compound c-1 as the component (C) at a ratio of 0.8 to the compound and the epoxy group of the compound a-1 as the component (D) at a ratio of 0.4. Is. The (W) epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Example 2-2] Alkali-developable resin composition No. (A) 10.0 g of compound a-1 as an epoxy compound, (B) 2.55 g of compound b as an unsaturated monobasic acid, 0.035 g of 2,6-di-t-butyl-p-cresol , 0.063 g of tetrabutylammonium chloride, and 8.36 g of PGMAc, and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour, and 120 ° C. for 17 hours. Cooled to room temperature, (C) 2.76 g and 1,2,3 of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter also referred to as compound c-2) as polybasic acid anhydride , 6-tetrahydrophthalic anhydride (hereinafter also referred to as compound c-3) 0.85 g, tetrabutylammonium chloride 0.057 g and PGMac 4.69 g were added, and the mixture was added at 120 ° C. for 5 hours, 90 ° C. for 1 hour, 60 After stirring at 40 ° C. for 2 hours and at 40 ° C. for 3 hours, 6.10 g of PGMAc was added to obtain the target alkali-developing resin composition No. 1 as a PGMAc solution. 1 (Mw = 6630, Mn = 2820, acid value (solid content) 92 mg · KOH / g). The obtained alkali developable resin composition No. 2 contained 44.5% by mass of the (X) photopolymerizable unsaturated compound as a reaction product.
In addition, alkali developable resin composition No. The (X) photopolymerizable unsaturated compound contained in 2 has a structure in which the compound (b) as the component (B) is added to the compound a-1 as the component (A), and the hydroxyl group 1 of the epoxy adduct (W). The compound (C) was obtained by an esterification reaction at a ratio of 0.295 compounds c-2 and 0.175 compounds c-3. The (W) epoxy adduct has a structure in which the carboxyl group of compound b is added at a ratio of 1.0 to one epoxy group of compound a-1.

[Example 2-3] Alkaline-developable resin composition No. Production of 3 Compound a-1 as an epoxy compound (A) 10.0 g, Compound b as an unsaturated monobasic acid (B) 2.55 g, 2,6-di-t-butyl-p-cresol 0.035 g , 0.063 g of tetrabutylammonium chloride, and 8.36 g of PGMAc, and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour, and 120 ° C. for 17 hours. After cooling to room temperature, 2.18 g of compound c-1 as polybasic acid anhydride (C) and 0.48 g of hexahydrophthalic anhydride (hereinafter also referred to as compound c-4), 0.056 g of tetrabutylammonium chloride And 3.89 g of PGMAc were added and stirred at 100 ° C. for 5 hours. Thereafter, the mixture was cooled to room temperature, 4.77 g of compound a-1 and 0.022 g of 2,6-di-t-butyl-p-cresol were added as an epoxy compound (D), 90 ° C. for 90 minutes, 120 ° C. For 4 hours and at 100 ° C. for 7 hours. Furthermore, 1.33 g of compound c-3 was added as polybasic acid anhydride (E), stirred at 100 ° C. for 3 hours, 13.1 g of PGMAc was added, and the alkali-developing resin composition as the target product as a PGMAc solution No. 3 was obtained (Mw = 7820, Mn = 3040, acid value (solid content) 49 mg · KOH / g). The obtained alkali developable resin composition No. 3 contained 44.4% by mass of the photopolymerizable unsaturated compound (Z) as a reaction product.
In addition, alkali developable resin composition No. 3 is a hydroxyl group 1 of an epoxy addition compound (W) having a structure in which a compound b as a component (B) is added to a compound a-1 as a component (A). Compound (D) is component (D) at a ratio of 0.7 acid anhydride structure of compound c-1 which is component (C) and 0.1 acid anhydride structure of compound c-4 In the ratio of 0.53 epoxy group of a-1 and the ratio of 0.28 acid anhydride structure of the compound c-3 which is the component (E), the epoxy addition compound (W) and the compound c-1 , Compound c-4, compound a-1 and compound c-3 were obtained. The epoxy addition compound (W) has a structure in which the carboxyl group of the compound b is added at a ratio of 1.0 to one epoxy group of the compound a-1.

[Comparative Example 2-1] Alkali-developable resin composition No. Production of 4 1,695 g of 1,1-bis (4-glycidyloxyphenyl) -1- (biphenylyl) -1-cyclohexylmethane (hereinafter also referred to as compound a-2), 443 g of compound b, 2,6-di- 6 g of t-butyl-p-cresol, 11 g of tetrabutylammonium chloride and 1425 g of PGMAc were charged and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 16 hours. The mixture was cooled to room temperature, 718 g of PGMAc, 482 g of compound c-1 and 25 g of tetrabutylammonium chloride were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 508 g of compound a-2 and 218 g of PGMac were added and stirred at 90 ° C. for 90 minutes and at 120 ° C. for 11 hours, and then 1463 g of PGMAc was added thereto to add the target alkali developing resin composition No. 1 as a PGMAc solution. 4 was obtained (Mw = 4200, Mn = 2200, acid value (solid content) 53 mg · KOH / g).

[Comparative Example 2-2] Alkali-developable resin composition No. 5 was charged with 390 g of compound a-2, 71.1 g of compound b, 1.34 g of 2,6-di-t-butyl-p-cresol, 1.75 g of tetrabutylammonium chloride, and 108 g of PGMac at 90 ° C. The mixture was stirred for 1 hour at 100 ° C for 1 hour, 110 ° C for 1 hour and 120 ° C for 17 hours. Cool to room temperature, add 59.2 g of compound c-2, 45.2 g of compound c-3, 4.08 g of tetrabutylammonium chloride, and 137 g of PGMac, add 120 ° C. for 5 hours, 90 ° C. for 1 hour, 60 After stirring at 40 ° C. for 2 hours and at 40 ° C. for 3 hours, 203 g of PGMAc was added, and the alkali-developable resin composition No. 1 as the target product as a PGMAc solution was added. 5 (Mw = 3700, Mn = 2000, acid value (solid content) 91 mg · KOH / g).

[Comparative Example 2-3] Alkali-developable resin composition No. Production of 6 9,9-bis (4-glycidyloxyphenyl) fluorene (hereinafter also referred to as compound a-3) 75.0 g, compound b 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g, and PGMAc 65.9 g were charged and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour, and 120 ° C. for 14 hours. The mixture was cooled to room temperature, 25.9 g of compound c-1, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMAc were added, and the mixture was stirred at 100 ° C. for 5 hours. Furthermore, 30.0 g of compound a-3, 2,69-di-t-butyl-p-cresol 0.269 g, and PGMac 1.50 g were added, and after stirring at 90 ° C. for 90 minutes and 120 ° C. for 4 hours, 93.4 g of PGMAc was added, and the comparative alkali-developable resin composition no. 6 (Mw = 4190, Mn = 2170, acid value (solid content) 52 mg · KOH / g).

[Comparative Example 2-4] Alkali-developable resin composition No. 7 Preparation of compound a-3 184 g, compound b 58.0 g, 2,6-di-t-butyl-p-cresol 0.26 g, tetrabutylammonium chloride 0.11 g and PGMac 23.0 g were charged at 120 ° C. For 16 hours. After cooling to room temperature, 35 g of PGMAc, 59.0 g of compound c-2 and 0.24 g of tetra-n-butylammonium bromide were added and stirred at 120 ° C. for 4 hours. Further, 20.0 g of compound c-3 was added, and after stirring at 120 ° C. for 4 hours, at 100 ° C. for 3 hours, at 80 ° C. for 4 hours, at 60 ° C. for 6 hours and at 40 ° C. for 11 hours, 90 g of PGMAc was added to obtain the desired product. Comparative alkali-developable resin composition no. 7 (Mw = 5000, Mn = 2100, acid value (solid content) 93 mg · KOH / g).

[Examples 3-1 to 3-2 and Comparative Examples 3-1 to 3-4] Alkali-developable photosensitive resin composition No. 1-No. Preparation of 6 To 44 g of the alkali-developable resin composition described in Table 3, 6.3 g of trimethylolpropane triacrylate and (F) 2.1 g of benzophenone and 78 g of PGMAc as a photopolymerization initiator were added and stirred well to obtain an alkali-developable feeling. Photopolymer composition No. 1-No. 6 was obtained.
The substrate was spin-coated with γ-glycidoxypropylmethylethoxysilane and spin-dried, and then the alkali-developable photosensitive resin composition was spin-coated (1300 rpm, 50 seconds) and dried. . After pre-baking at 70 ° C. for 20 minutes, a 5% polyvinyl alcohol solution was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, using a predetermined mask and exposing using an ultrahigh pressure mercury lamp as a light source, developed by immersing in a 2.5% sodium carbonate solution at 25 ° C. for 30 seconds, and thoroughly washed with water. . After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The following sensitivity, resolution, and adhesion were evaluated for the obtained pattern. The results are shown in [Table 3].

<Sensitivity>
During exposure, what exposure was sufficient 70 mJ / cm ² a, inadequate in 70 mJ / cm ^2, those exposed at 100 mJ / cm ² b, insufficient in 100mJ / cm ^2, 150mJ / cm ^The one exposed in ² was designated as c.
<Resolution>
At the time of exposure and development, A can be formed with a good pattern even with a line width of 8 μm or less, B can be formed with a good pattern if the line width is 10 μm, and a good pattern cannot be formed unless the line width is 30 μm or more. Was evaluated as C.
<Adhesion>
The peeling of the pattern obtained by development was visually observed. The pattern peeling was not observed at all, and the pattern peeling was partially observed as x.

  In Examples 3-1 and 3-2, the alkali-developable photosensitive resin composition No. 1 and no. 2 is the alkali-developable photosensitive resin composition No. used in Comparative Examples 3-1 to 3-4. 3-No. The sensitivity was higher than 6, and the resolution and adhesion were excellent.

[Examples 4-1 to 4-2 and Comparative Examples 4-1 to 4-4] Colored alkali-developable photosensitive resin composition Nos. 1-No. Preparation of 6 With respect to 44 g of the alkali-developable resin composition shown in Table 4, 8.0 g of trimethylolpropane triacrylate, (F) 1.8 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photopolymerization initiator, G) 3.2 g of MA100 (carbon black, manufactured by Mitsubishi Chemical Corporation) and 75 g of PGMAc as colorants were added and stirred well, and the colored alkali-developable photosensitive resin composition No. 1-No. 6 was obtained.
The obtained colored alkali-developable photosensitive resin composition No. 1-No. 6 was evaluated in the same manner as in Example 3-1. The results are shown in [Table 4].

  The colored alkali-developable photosensitive resin composition No. of Examples 4-1 and 4-2. 1 and no. 2 is the colored alkali-developable photosensitive resin composition No. 2 used in Comparative Examples 4-1 to 4-4. 3-No. The sensitivity was higher than 6, and the resolution and adhesion were excellent.

Claims (9)

An epoxy compound represented by the following general formula (1):

(Wherein, X is C androgenic optionally substituted alkyl group having 1 to 10 carbon atoms in the atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, substituted with a halogen atom An arylalkyl group having 7 to 20 carbon atoms which may be substituted, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom , Y being substituted with a halogen atom; An alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms which may be substituted with a halogen atom, and an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom Or a halogen atom , Z ¹ and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or a halogen atom;
The methylene group in the alkyl group, aryl group, and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, under the condition that they are not adjacent to each other, and X is a ring of X together. May be formed,
L ¹ is a 1,2-ethanediyl group or a 1,2-propanediyl group, n represents a number of 1 to 5 , and when n is 2 or more, a unit represented by [L ¹ O] _n is , A random copolymer or block copolymer of an ethyleneoxy group and a propyleneoxy group may be used,
k represents a number of 0 to 4, p represents a number of 1 or 2 , r and s each independently represent a number of 0 or 1 , and when k or p is 2 or more, a plurality of X or Y may be the same or different, x is 2, y is Ru 0 der. ) Epoxy compounds of claim 1 represented by the following general formula (2).

(In the formula, X, Y, Z ¹ , Z ² , L ¹ , n, k, r and s are the same as those in the general formula (1).) The polymerizable composition characterized by containing an epoxy compound according to claim 1 or 2. (A) An epoxy addition compound having a structure in which (B) an unsaturated monobasic acid is added to the epoxy compound according to claim 1 or 2 . (W) containing (X) a photopolymerizable unsaturated compound having a structure which is a reaction product obtained by an esterification reaction between the epoxy addition compound according to claim 4 and (C) a polybasic acid anhydride. An alkali-developable resin composition characterized by that. (W) (X) a photopolymerizable unsaturated compound having a structure which is a reaction product obtained by an esterification reaction between the epoxy addition compound according to claim 4 and (C) a polybasic acid anhydride; (D) An alkali-developable resin composition comprising (Y) a photopolymerizable unsaturated compound having a structure which is a reaction product obtained by adding an epoxy compound. (W) (X) a photopolymerizable unsaturated compound having a structure which is a reaction product obtained by an esterification reaction between the epoxy addition compound according to claim 4 and (C) a polybasic acid anhydride; (D) A reaction product obtained by subjecting (E) a photopolymerizable unsaturated compound having a structure, which is a reaction product obtained by adding an epoxy compound, to an esterification reaction of (E) a polybasic acid anhydride. An alkali-developable resin composition comprising (Z) a photopolymerizable unsaturated compound having a structure of: An alkali-developable photosensitive resin composition comprising the alkali-developable resin composition according to any one of claims 5 to 7 and (F) a photopolymerization initiator. A colored alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition according to claim 8 and further containing (G) a coloring material.