JP5385729B2 - Photosensitive resin - Google Patents

Description

  The present invention includes, for example, a black matrix for manufacturing a liquid crystal display panel, a color filter, a photo spacer, a color filter used for an organic EL display capable of color display using a transparent protective film and an organic EL element, and a color filter using an inkjet. It is related with the photosensitive resin which can be used as a photosensitive resin material applicable when producing this.

In recent years, radiation curable resins that can be cured with ultraviolet rays or electron beams have been widely used in the fields of printing, paints, and adhesives from the viewpoint of resource saving and energy saving.
In the field of electronic devices such as printed wiring boards, solder resist is used for protecting circuit boards after mounting components for a long period of time. Acid pendant type novolak epoxy acrylate is generally used as a material for printed wiring boards by the photoresist method, but the adhesion to copper plating is not sufficient, and when used for multilayer printed wiring boards, it is a conductor. In addition to the problem that sufficient adhesion strength between the circuits cannot be obtained, there is also a problem that it is easy to break due to poor flexibility.
In order to solve these problems, a method of mixing an inorganic filler into a photosensitive resin composition using a (meth) acrylic copolymer has been proposed (for example, Patent Document 1), but an acid pendant novolak epoxy acrylate is proposed. However, the problem of poor heat resistance remained.

  Color filters are used in color liquid crystal display devices and solid-state image sensors, and these are colored colors in which three colors of red (R), green (G), and blue (B) are formed in a predetermined pattern on a substrate. It consists of a coating film and a black black matrix between these three color filters of RGB. Usually, a black matrix is formed on a transparent substrate such as glass, and then R, G, and B patterns are sequentially formed.

In general, color filters include production methods such as a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. Among these, in particular, a photocurable resin composition mainly composed of an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a pigment and a solvent is used, applied onto a transparent substrate, and exposed, developed, and postcured. The pigment dispersion method created by the repeated photolithographic method is currently mainstream because it has excellent durability such as light resistance and heat resistance and has few defects such as pinholes.
While the pigment dispersion method has the above-mentioned advantages, the pattern of black matrix, R, G, and B is repeatedly formed, so that high heat resistance is required for the alkali-soluble resin that becomes the binder of the coating film.

Conventionally, as a method for improving heat resistance, a resin composition (for example, Patent Document 2) containing a (meth) acrylic acid ester having a cyclic structure in the side chain as a copolymerization component, or a monomer containing maleimide is used. A resin composition (for example, Patent Document 3) or the like as a polymerization component has been proposed.
However, in the former resin composition with (meth) acrylic acid ester having a cyclic structure in the side chain as a copolymerization component, the side chain is thermally decomposed during post-curing and becomes a volatile component, which contaminates the production line. There was a problem to do. In addition, the resin composition having the latter maleimide-containing monomer as a copolymerization component has a yellow to yellow-brown color caused by nitrogen atoms contained in the molecule, and the transparency of the coating film is improved. make worse. Furthermore, there has been a problem that coloring progresses during post-curing after heat treatment.

In order to solve the above technical problem, the present applicant has developed a photosensitive resin composition using a resin prepared from a specific monomer having a cyclic structure and a crosslinked structure and a compound such as an unsaturated monobasic acid ( Patent Documents 4 and 5).
However, even such a resin may have insufficient performance as a photosensitive resin.

JP 2006-190848 A JP 2004-240396 A JP 2003-029018 A JP 2008-076860 A JP 2001-089533 A

  The inventors of the present application are photosensitive resins that can be used for color filters and the like, and that have further superior performance than conventional ones, in particular, photosensitive resins with high exposure sensitivity, good pigment dispersibility, and good developability with an alkaline aqueous solution. An object is to obtain a functional resin.

As a result, the inventors of the present application obtained the photosensitive resin shown below. In particular,
(I) The radically polymerizable compound (a) containing a glycidyl group is copolymerized with 5 to 95 mol%, and the radically polymerizable compound (b) capable of copolymerizing with the (a) (5) to 95 mol%, Obtaining a copolymer comprising (a) and (b),
(Ii) The compound (c) represented by the following formula (1) and (meth) acrylic acid are added to 90 to 100% of the glycidyl group contained in the copolymer, and this is represented by the following formula (1). The amount of the compound (c) added is 5 to 50% of the glycidyl group contained in the copolymer,
(Iii) Furthermore, the polybasic acid anhydride (d) is added to 5 to 100% of the hydroxyl group produced when the compound (c) represented by the following formula (1) and (meth) acrylic acid are added. Obtained photosensitive resin (A)

(R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in chemical formula (1) each represent a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group, and R ₆ represents a hydrogen atom, a methyl group or a phenyl group. It is shown.)

  The photosensitive resin (A) of the present invention includes, for example, a solder resist for manufacturing a printed wiring board, an electroless plating resist, an insulating layer or a wide printing plate of a build-up method printed wiring board, a liquid crystal display material, a plasma display, an organic It can be used as a photosensitive material for an EL display, has high exposure sensitivity, and good developability with an alkaline aqueous solution. The cured product after development is a photosensitive material capable of forming a cured coating film excellent in electrical characteristics, mechanical characteristics, heat resistance, chemical resistance and the like.

The present invention is described in detail below.
The radically polymerizable compound (a) containing a glycidyl group used in the present invention is not particularly limited. For example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy, and the like. Lactone adduct [e.g., Cyclomer A200, M100 manufactured by Daicel Chemical Industries, Ltd.], mono (meth) acrylate ester of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, dicyclopentenyl (Meth) acrylate epoxidized product, dicyclopentenyloxyethyl (meth) acrylate epoxidized product, and the like. Glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) are easily available. Acrylate is preferred Used frequently. One or two or more of these may be used in combination.

  In the present invention, the radically polymerizable compound (b) that can be copolymerized with (a) is not particularly limited as long as it has an ethylenically unsaturated group. Specific examples thereof include dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and iso-propyl (meth) acrylate. , N-butyl (meth) acrylate, sec-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) relate, lauryl (meth) acrylate, dodecyl (meth) ) Acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (acrylate, neopentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, hex (Meth) acrylate, 2-ethylhexyl (meth) acmeta) acrylate, ethylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, tricyclodecanyl (meth) acrylate, Tricyclodecanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) ) Acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate Rate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl ( (Meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylic esters such as glyceryl mono (meth) acrylate, butanetriol mono (meth) acrylate, pentanetriol mono (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate; (meth) acrylic acid Amides, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di-iso -(Meth) acrylic amides such as propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride , N-vinylpyrrolidone, vinylpyri Vinyl compounds such as styrene and vinyl acetate; styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Unsaturated dicarboxylic acid diesters; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; N- (meth) acryloylphthalimide, and norbornene (bicyclo [2 2.1] hept-2-ene), dicyclopentadiene, 5-norbornene-2,3-dicarboxylic acid anhydride, rosin (meth) acrylate, and the like. Of these, benzyl (meth) acrylate, tricyclodecanyl (meth) acrylate, vinyltoluene, norbornene, rosin (meth) acrylate, and monomaleimides are preferably used from the viewpoints of adhesion and heat resistance of the cured coating film. Particularly preferably, tricyclodecanyl (meth) acrylate (for example, trade names FA-513A and FA-513M manufactured by Hitachi Chemical Co., Ltd.), norbornene, rosin (meth) acrylate (for example, 2- Hydroxypropyl dehydroabietic acid acrylate “Beamset 101”, “Beamset 102”, “Beamset 115”, “K1000A” and “UNIRESIN K900B” manufactured by Shin-Nakamura Chemical Co., Ltd.), vinyltoluene. These may be used alone or in combination of two or more.

  The compound (c) used in the present invention is represented by the following formula (1), and by using this compound, it is excellent in heat resistance and sensitivity, and is further excellent in pigment dispersibility.

(R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in chemical formula (1) each represent a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group, and R ₆ represents a hydrogen atom, a methyl group or a phenyl group. Show.)

  Specific examples of the above formula (1) include cinnamic acid, 2,3,4-trimethoxycinnamic acid, 2,4,5-trimethoxy cinnamic acid, 3,4,5-trimethoxy cinnamic acid. 2,4-dimethoxycinnamic acid, 2,5-dimethoxycinnamic acid, 3,4-dimethoxycinnamic acid, o-, m-, p-methylcinnamic acid, 3,4-methylenedioxycinnamic acid 3,5-dimethoxy-4-hydroxycinnamic acid, 3-hydroxy-4-methoxycinnamic acid, o-, m-, p-methoxycinnamic acid, α-methylcinnamic acid, α-phenylcinnamic acid However, it is not limited to this.

The polybasic acid anhydride (d) used in the present invention is not particularly limited. For example, succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, endomethylene Examples include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like.
Of these, tetrahydrophthalic anhydride and succinic anhydride are preferably used. One or more of these may be used in combination.

In order to obtain the photosensitive resin (A) of the present invention, first, a copolymer consisting of a radically polymerizable compound (a) containing a glycidyl group and a radically polymerizable compound (b) that can be copolymerized with the above (a). A coalescence is prepared.
The composition ratio of the radically polymerizable compound (a) containing a glycidyl group and the radically polymerizable compound (b) copolymerizable with the above (a) is 5 to 95 mol%, preferably (a) is The amount is 20 to 80 mol%, and the total amount is 100 mol%. The total amount of the compound (c) represented by the above formula (1) and (meth) acrylic acid added is determined by the amount of the radical polymerizable compound (a) containing a glycidyl group at this time. By reducing the amount of the radically polymerizable compound (a) containing a glycidyl group to 5 mol% or more, a decrease in the double bond amount can be suppressed, and by setting it to 95 mol% or less, the above formula (1) Gelation at the time of addition of the compound (c) and (meth) acrylic acid shown is suppressed.

  Next, the total amount of the compound (c) represented by the above formula (1) and (meth) acrylic acid added is 90 to 100%, preferably 95, based on the glycidyl group contained in the obtained copolymer. % To 100%. If it is less than 90%, high molecular weight or gelation tends to occur upon addition of the polybasic acid anhydride due to the influence of the remaining glycidyl group, and if it exceeds 100%, the unreacted compound (c) represented by the above formula (1) Further, the amount of (meth) acrylic acid increases, which causes an outgas during post-baking, which is not preferable.

The compound (c) is added in such an amount that 50% or less, preferably 40% or less, of the glycidyl group contained in the copolymer is reacted with the carboxyl group of the compound (c) represented by the above formula (1). That is, the compound (c) is added so that the carboxyl group of the compound (c) is reacted with 1 equivalent of the glycidyl group of the copolymer in an amount of 0.5 equivalent or less, preferably 0.4 equivalent or less. . The lower limit of the addition amount of the compound (c) is not particularly limited as long as it is 5% or more, but is preferably 7% or more, more preferably 10% or more of the glycidyl group contained in the copolymer. is there. If it is less than 5%, effects such as sensitivity and heat resistance may not be sufficient. Moreover, pigment dispersibility improves by setting it as 5% or more. This is considered that the dispersion stability of the pigment was improved by introducing an aromatic ring into the side chain and interacting with the pigment.
By making the addition amount of a compound (c) 50% or less of the glycidyl group contained in the said copolymer, it can prevent that the balance of heat resistance, heat yellowing resistance, and solvent resistance is lost.

  Further, the addition amount of the polybasic acid anhydride (d) is 5 to 100% of the hydroxyl group produced when the compound (c) represented by the above formula (1) and (meth) acrylic acid are added, preferably It is 10 to 90%, more preferably 15 to 80%. By setting the addition amount of the polybasic acid anhydride (d) in the range of 5 to 100% of the hydroxyl group produced when the compound (c) represented by the above formula (1) and (meth) acrylic acid are added. The acid value (JIS K6901) of the photosensitive resin (A) can be controlled in the range of 20 to 180 KOHmg / g.

  The molecular weight of the photosensitive resin (A) is 3000 to 50000, preferably 5000 to 30000, in terms of polystyrene weight average molecular weight. When the molecular weight is 3000 or more, a decrease in heat resistance can be prevented, and when the molecular weight is 50000 or less, a decrease in developability can be prevented.

  A photosensitive resin composition is obtained by adding a photopolymerizable monomer (B), a photopolymerization initiator (C), and a solvent (D) to the photosensitive resin (A) obtained as described above.

  The photopolymerizable monomer (B) that can be used is not particularly limited as long as it can react with the photosensitive resin. For example, aromatic vinyl monomers such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallylphthalate, diallylbenzenephosphonate; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, trimethylol propane di (meth) acrylate, trimethylol prop (Meth) acrylic monomers such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate; triallyl cyanurate, etc. Can be mentioned. One or more of these may be used in combination.

The addition amount of the photopolymerizable monomer (B) is usually 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the photosensitive resin.
By setting it as the said range, photocurability can be maintained in an appropriate range, and also a viscosity can be adjusted.

As the solvent (D) that can be used, any inert solvent that does not react with the photosensitive resin (A) and the photopolymerizable monomer (B) can be used without limitation.
Usable solvents (D) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol Examples thereof include monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate and the like. Among these, propylene glycol monomethyl ether acetate preferably used in the radical polymerization reaction is preferably used.

The amount of the solvent (D) added is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass with respect to 100 parts by mass of the photosensitive resin (A).
By setting it as the said range, a viscosity can be kept moderate.

  When the photosensitive resin composition is photocured using active light such as ultraviolet rays as active energy rays, a photopolymerization initiator (C) is added. Although it does not specifically limit as a photoinitiator (C) which can be utilized, For example, benzoin and its alkyl ethers, such as benzoin, benzoin methyl ether, benzoin ethyl ether; acetophenone, 2, 2- dimethoxy-2-phenyl acetophenone, Acetophenones such as 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like Anthraquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenones such as zophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; acylphosphine oxides and xanthones. One or two or more of these may be used in combination.

  The compounding quantity of a photoinitiator (C) is 0.1-30 mass parts normally with respect to 100 mass parts of solid content in this photosensitive resin composition, Preferably, 0.5-20 mass parts, Furthermore, Preferably, it is 1-10 mass parts. By setting it as 0.1-30 mass parts, photocurability can be maintained in an appropriate range.

  Furthermore, this photosensitive resin composition can contain a well-known coloring agent, an antifoamer, a coupling agent, a leveling agent, etc. as needed.

  As described above, since this photosensitive resin has an acid value of 20 to 180 KOHmg / g, resists using the photosensitive resin composition containing them can be developed using an aqueous alkali solution.

  This photosensitive resin composition is applied, for example, on a printed wiring board by a screen printing method, a roll coater method, a curtain coater method, a spray coater method, a spin coat method, etc. Development is performed by washing away the hardened (unexposed) portion with an alkaline aqueous solution.

  As an aqueous alkali solution used for development, an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide or the like, or an amine type, an aminophenol type compound is also useful, but a p-phenylenediamine type compound is preferably used. Representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N- Examples include ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and aqueous solutions of these sulfates, hydrochlorides or p-toluenesulfonates. It is done.

  As a light source used for curing the coated surface by light irradiation, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metahalide lamp, or the like is used.

  In addition, the above-mentioned photosensitive resin composition is, for example, a solder resist for manufacturing a printed wiring board, an electroless plating resist, an insulating layer of a build-up method printed wiring board or a wide range of printing plates, liquid crystal display materials, plasma displays, organic It can be used as a photosensitive material for an EL display, has high exposure sensitivity, and good developability with an alkaline aqueous solution. The cured product after development is a photosensitive material capable of forming a cured coating film excellent in electrical characteristics, mechanical characteristics, heat resistance, chemical resistance and the like.

  Furthermore, thermosetting is possible by blending a known epoxy resin and a curing accelerator, and it is also applicable to thermosetting ink jet methods.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited at all by these examples.
In addition, the molecular weight of each resin is a polystyrene equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography).

(Synthesis Example 1)
328.9 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while purging with nitrogen, and heated to 120 ° C.
Next, t- was added to a monomer mixture composed of 66.0 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 11.8 parts by mass of vinyltoluene, and 85.2 parts by mass of glycidyl methacrylate. 16.3 parts by mass of butyl peroxy-2-ethylhexanoate [Nippon Yushi Co., Ltd., Perbutyl O] was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 35.4 parts by mass of acrylic acid, 13.3 parts by mass of cinnamic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were mixed with the above copolymer. The reaction was continued at 120 ° C., and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 19.0 parts by mass of succinic anhydride was added and reacted at 115 ° C. for 2 hours to obtain a photosensitive resin solution having a solid content acid value of 45.1 KOH mg / g, a weight average molecular weight of 7000, and a resin solid content of 42.0%. Obtained.

(Synthesis Example 2)
In the same reactor as in Synthesis Example 1, 331.5 parts by mass of propylene glycol monomethyl ether acetate was taken, stirred while replacing with nitrogen, and heated to 120 ° C.
Next, 9.3 parts by mass of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture composed of 9.4 parts by mass of norbornene, 23.6 parts by mass of vinyltoluene, and 99.4 parts by mass of glycidyl methacrylate. . This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 43.9 parts by mass of acrylic acid, 10.4 parts by mass of cinnamic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were added to the above copolymer. The reaction was continued at 120 ° C., and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 64.6 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours, whereby a photosensitive resin solution having a solid content acid value of 95.3 KOHmg / g, a weight average molecular weight of 10,000, and a resin solid content of 42.0%. Got.

(Synthesis Example 3)
In the same reactor as in Synthesis Example 1, 339.0 parts by mass of propylene glycol monomethyl ether acetate was taken, stirred while being purged with nitrogen, and heated to 120 ° C.
Next, 5.3 parts by mass of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture composed of 9.4 parts by mass of norbornene, 23.6 parts by mass of vinyltoluene, and 99.4 parts by mass of glycidyl methacrylate. . This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 28.7 parts by mass of acrylic acid, 41.4 parts by mass of cinnamic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were added to the above copolymer. The reaction was continued at 120 ° C., and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 58.5 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours, whereby a photosensitive resin solution having a solid content acid value of 84.4 KOH mg / g, a weight average molecular weight of 18000, and a resin solid content of 42.0%. Got.

(Synthesis Example 4)
In the same reactor as in Synthesis Example 1, 402.3 parts by mass of propylene glycol monomethyl ether acetate was taken, stirred while replacing with nitrogen, and heated to 120 ° C.
Next, t-butylperoxy-2-l was added to a monomer mixture composed of 43.0 parts by mass of rosin acrylate [Arakawa Chemical Industries, Ltd. Beam Set 101], 17.6 parts by mass of benzyl methacrylate, and 113.6 parts by mass of glycidyl methacrylate. 7.0 parts by weight of ethyl hexanoate was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 53.0 parts by mass of acrylic acid, 5.9 parts by mass of cinnamic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were added to the above copolymer. The reaction was continued at 120 ° C., and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 76.0 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours to give a photosensitive resin solution having a solid content acid value of 92.1 KOH mg / g, a weight average molecular weight of 17000, and a resin solid content of 42.0%. Got.

(Comparative Synthesis Example 1)
In the same reaction apparatus as in Synthesis Example 1, 344.2 parts by mass of propylene glycol monomethyl ether acetate was taken, stirred while being purged with nitrogen, and heated to 120 ° C.
Next, 11.1 parts by mass of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture composed of 88.0 parts by mass of benzyl methacrylate and 71.0 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 13.3 parts by mass of acrylic acid, 44.4 parts by mass of cinnamic acid, 0.8 parts by mass of triphenylphosphine, and 0.2 parts by mass of methylhydroquinone were mixed with the above copolymer. The reaction was continued at 120 ° C., and the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 42.6 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours, whereby a photosensitive resin solution having a solid content acid value of 60.3 KOH mg / g, a weight average molecular weight of 9000 and a resin solid content of 42.0%. Got.

(Comparative Synthesis Example 2)
In the same reaction apparatus as in Synthesis Example 1, 350.4 parts by mass of propylene glycol monomethyl ether acetate was taken, stirred while replacing with nitrogen, and heated to 120 ° C.
Next, 10.9 parts by mass of t-butylperoxy-2-ethylhexanoate was added to a monomer mixture composed of 70.4 parts by mass of benzyl methacrylate and 85.2 parts by mass of glycidyl methacrylate. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 41.9 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, and 120 ° C. And the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 66.9 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours, whereby a photosensitive resin solution having a solid content acid value of 93.5 KOH mg / g, a weight average molecular weight of 10,000, and a resin solid content of 42.0%. Got.

(Comparative Example Synthesis Example 3)
In the same reactor as in Synthesis Example 1, 357.1 parts by mass of propylene glycol monomethyl ether acetate was taken, stirred while replacing with nitrogen, and heated to 120 ° C.
Next, a monomer mixture comprising 66.0 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), 17.6 parts by mass of benzyl methacrylate, and 85.2 parts by mass of glycidyl methacrylate was added to t- 18.6 parts by mass of butyl peroxy-2-ethylhexanoate [Nippon Yushi Co., Ltd., Perbutyl O] was added. This was added to the flask from the dropping funnel over 2 hours and further stirred at 120 ° C. for 2 hours to obtain a copolymer solution.
Next, the inside of the flask was replaced with air, and 41.9 parts by mass of acrylic acid, 0.8 part by mass of triphenylphosphine, and 0.2 part by mass of methylhydroquinone were charged into the solution of the above copolymer, and 120 ° C. And the reaction was terminated when the acid value of the solid content reached 0.8 KOH mg / g. Next, 59.3 parts by mass of tetrahydrophthalic anhydride was added and reacted at 115 ° C. for 2 hours to give a photosensitive resin solution having a solid content acid value of 76.1 KOHmg / g, a weight average molecular weight of 7000, and a resin solid content of 42.0%. Got.

[Example 1 to Example 4, Comparative Example 1 to Comparative Example 3]
Each component shown below was mix | blended using the photosensitive resin obtained from the synthesis examples 1-4 and the comparative synthesis examples 1-3, and each photocurable resin composition was obtained. The compositions using Synthesis Examples 1, 2, 3, 4 and Comparative Synthesis Examples 1, 2, 3 are referred to as Examples 1, 2, 3, 4 and Comparative Examples 1, 2, 3, respectively.

<Transparent resist resin cured product>
A resin composition prepared by adding 30 parts by mass of pentaerythritol tetraacrylate and 4 parts by mass of 2,2-dimethoxy-2-phenylacetophenone as a photopolymerization initiator to 100 parts by mass of the solid content of each photosensitive resin solution. Apply it to a glass substrate with a thickness of 10 μm when wet using an applicator, volatilize the low-boiling substances in a warm air dryer at 100 ° C., and then use an ultra-high pressure mercury lamp manufactured by Oak Manufacturing Co., Ltd. as necessary. The film was exposed at 50 mJ / cm ² to obtain a cured coating film having a thickness of 2 μm, and then alkali development was performed.

(1) Heat resistance Each cured coating film was cut out and subjected to thermogravimetric analysis (TGA). The cut sample was heated to 220 ° C., and the weight change rate when held for 2 hours was measured.
(2) Heat-resistant discoloration The coating film formed on the glass substrate was left in a dryer at 230 ° C. for 1 hour, and the coloring of the coating film before and after the heat treatment was compared with a color difference meter.
○: ΔE · ab is less than 0.3 ×: ΔE · ab is 0.3 or more

(3) Transparency The coating film formed on the glass substrate was left in a dryer at 230 ° C. for 1 hour, and the light transmittance at 400 nm of the coating film before and after the heat treatment was measured with a spectrophotometer.
○: Change rate of transmittance is less than 1% ×: Change rate of transmittance is 1% or more (4) Adhesion A cross-cut test is performed on the cured coating film according to JIS K5400, and 100 cross-cuts are peeled off Was visually observed and evaluated according to the following criteria.
○: No separation was observed.
Δ: Peeling is observed in less than 10% of the whole.
X: Exfoliation is recognized in 10% or more of the whole.

Color resist (pigment type)
<Composition of pigment dispersion>
(Adjustment of green pigment dispersion)
・ C. I Pigment Green 36: 10.00 parts by mass / solvent (PGMAc): 33.75 parts by mass / dispersing agent: 6.25 parts by mass / zirconia beads having a diameter of 0.5 mm: 180 parts by mass (dispersed by a paint shaker for 3 hours)

<Create color resist cured coating>
A color resist is spin-coated on a 5 cm square glass substrate (non-alkali glass) to a film thickness of 2.2 μm when dried, prebaked at 80 ° C. for 3 minutes, and then a photomask is placed at a distance of 100 μm from the coating film. And exposed at 150 mJ / cm ² . Next, spray development was performed with a 0.11 mass% aqueous sodium carbonate solution at a water pressure of 0.3 MPa, and post baking was performed at 230 ° C. for 30 minutes to obtain a cured color resist coating film.

(5) Alkali developability time and residue The cured coating film exposed through the mask was spray-developed using a 0.1% aqueous sodium carbonate solution at 23 ° C., and the time when the pattern was completely visible and the residue after development were The presence or absence was evaluated visually.
○: There is no residue visually. X: There is residue visually. (6) Development Form In the development process of the negative resist, the uncured unexposed portion of the resist layer is dissolved by the alkali developer and detached from the substrate. However, as development forms, there are a peeling type in which the part to be separated mainly peels off as a large lump, and a dissolution type in which the dye is gradually dissolved and diffused so as to dissolve in water. The former peeling type is a development mode that is not preferred because the solid-liquid mass remains in the system as a foreign substance and easily contaminates the pixels of other colors, and the latter dissolution type is a development type that the latter is desired. .
×: Peeling type ○: Dissolving type

(7) Sensitivity The cured coating film exposed through the mask was subjected to spray development for 30 seconds using a 0.1% aqueous sodium carbonate solution at 23 ° C., and the amount of film loss before and after alkali development was measured. The smaller the film loss, the better the sensitivity.
○: Less than 0.20 μm ×: 0.20 μm or more (8) Solvent resistance In preparing a color resist cured coating film, a cured coating film was formed in the same manner as (7) except that front exposure was performed without using a photomask. Produced. Next, 200 ml of n-methyl-2-pyrrolidone was placed in a 500 ml glass bottle capable of being covered, and the cured coating film was immersed therein, and the color change after 23 ° C.-60 minutes was compared with a color difference meter.
○: ΔE · ab is less than 0.3 ×: ΔE · ab is 0.3 or more

(9) Viscosity change rate As a measure of pigment dispersion stability, the viscosity change of the colored resin composition was measured. When the pigment dispersion stability is poor, the viscosity increases, which is not preferable. This will be specifically described below.
The viscosity of the colored resin composition excluding the photoinitiator system component 1 and the photoinitiator system component 2 was measured immediately after adjustment and after standing in a thermostatic bath at 23 ° C. for 7 days (E-type viscometer). As a measure of good pigment dispersion stability, the viscosity change after 7 days is 10% or less, preferably 5% or less with respect to the initial viscosity.
○: 5% or less Δ: 10% or less ×: Greater than 10%

Claims (6)

(I) The radically polymerizable compound (a) containing a glycidyl group is copolymerized with 5 to 95 mol%, and the radically polymerizable compound (b) capable of copolymerizing with the (a) (5) to 95 mol%, Obtaining a copolymer comprising (a) and (b),
(Ii) The compound (c) represented by the following formula (1) and (meth) acrylic acid are added to 90 to 100% of the glycidyl group contained in the copolymer, and this is represented by the following formula (1). The amount of the compound (c) added is 5 to 50% of the glycidyl group contained in the copolymer,
(Iii) Furthermore, the polybasic acid anhydride (d) is added to 5 to 100% of the hydroxyl group produced when the compound (c) represented by the following formula (1) and (meth) acrylic acid are added. Obtained photosensitive resin (A).

(R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in chemical formula (1) each represent a hydrogen atom, a hydroxyl group, a methyl group or a methoxy group, and R ₆ represents a hydrogen atom, a methyl group or a phenyl group. Show.)   The radically polymerizable compound (b) that can be copolymerized with the (a) is selected from the group consisting of benzyl (meth) acrylate, tricyclodecanyl (meth) acrylate, vinyltoluene, norbornene, rosin (meth) acrylate, and monomaleimide. The photosensitive resin (A) of Claim 1 containing the compound which is 1 type (s) or 2 or more types selected. The photosensitive resin (A) according to claim 1 or 2, wherein glycidyl (meth) acrylate is used as the radically polymerizable compound (a) containing a glycidyl group . The photosensitive resin composition containing the photosensitive resin (A) in any one of Claims 1-3, a photopolymerizable monomer (B), a photoinitiator (C), and a solvent (D). The photopolymerizable monomer (B) is 10 to 200 parts by mass and the solvent (D) is 30 to 1000 parts by mass with respect to 100 parts by mass of the photosensitive resin (A), and the solid content in the photosensitive resin composition is 100. The photosensitive resin composition of Claim 4 whose photoinitiator (C) is 0.1-30 mass parts with respect to a mass part. A cured product obtained by curing the photosensitive resin composition according to claim 4.