TWI432897B - Photosensitive resin and cured resin thereof, and process for manufacturing photosensitive resin - Google Patents

Description

Photosensitive resin composition, cured product thereof, application thereof, and method for producing photosensitive resin

The present invention relates to a photosensitive resin composition having a carboxyl group-containing photosensitive urethane resin and a cured product thereof, which are useful for use in a printed wiring board, and the like, and a method for producing the above-mentioned photosensitive resin. More specifically, it is useful as a solder resist for a flexible printed wiring board, a plating resist, an interlayer electrical insulating material for a multilayer printed wiring board, a photosensitive optical waveguide, etc., and is excellent in developability and can be imparted to the cured film. A photosensitive resin composition having a photosensitive urethane resin containing a specific carboxyl group and a cured product thereof, which are excellent in adhesion, flexibility (bending property), solder heat resistance, chemical resistance, electrical insulation, and the like And a method of producing the above photosensitive resin. Further, it relates to a photosensitive solder resist ink and a dry film type photosensitive solder resist which are highly flame-retardant containing the above-mentioned photosensitive resin composition.

In the soldering step performed when the wiring (circuit) pattern formed on the substrate is protected from the external environment or when the electronic component is mounted on the printed wiring board, in order to prevent the solder from adhering to an unnecessary portion The protection is applied to a printed wiring board by a protective layer called a coverlay or a solder mask. In particular, in terms of a protective layer used for a wiring pattern formed on a polyimide film of a flexible printed wiring board, adhesion to a polyimide, flexibility, and folding resistance are required.

In the past, there was a pattern in which a metal mold which is a pattern of a polyimide film called a cover film which is a protective layer for a flexible printed wiring board was punched, and a bonding method was used, and a bonding method was used. Printed by screen A thermosetting ink that has been applied by brushing, etc., but with high density and high precision due to advances in electronic products in recent years, it is possible to review the ultraviolet curable resist type solder resist which can be patterned with higher precision. Ink or dry film solder resist.

In general, regarding an optical solder resist for a flexible printed wiring board, it is known that pattern precision can be obtained in terms of an optical solder resist used for a rigid substrate, however, the cured coating film is hard and aggregated. The adhesion of quinone imine is not good, and sufficient flexibility, flexibility, and folding resistance are not obtained.

In view of the above, a large number of optical solder resists having flexibility have been proposed in recent years. For example, a resist ink composition containing a resin which reacts succinic anhydride in an addition product of an epoxy resin having a bisphenol A skeleton in a main chain and a monocarboxylic acid having an unsaturated group is disclosed (Patent Literature) 1). This is excellent in developability, light sensitivity, adhesion, heat resistance, and the like, but there are still insufficient problems in terms of flexibility and folding endurance. Further, as a photosensitive thermosetting composition, a reaction of a secondary hydroxyl group formed by an esterification reaction of a cresol novolak epoxy compound with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride has been proposed. The product is a reaction product of the same two-stage hydroxyl group and an isocyanate compound containing an unsaturated group (Patent Document 2). These are excellent in adhesion, solder heat resistance, and coating film resistance, but there are still insufficient problems in terms of flexibility and folding endurance.

In addition, a photosensitive component which is obtained by copolymerizing a monomer containing (meth)acrylic acid and (meth)acrylic acid ester and using the obtained polymer as a binder component is proposed (Patent Document 3). These are excellent in developability and resolution. However, when used in the use of a flexible printed wiring board, sufficient adhesion, flexibility, and folding resistance are not obtained.

Further, it is proposed to react a polyol compound with a polybasic acid anhydride having two acid anhydride groups in the molecule to form a carboxyl group-containing polyester polyol having a half-esterified ester bond in the main chain, and The polyisocyanate compound is reacted to obtain a carboxyl group-containing ethyl urethane prepolymer, further to the partial carboxyl group in the urethane prepolymer, and having an epoxy group in the molecule (methyl group) A photosensitive resin composition containing a carboxyl group-containing urethane oligomer obtained by the reaction of an acrylate (Patent Document 4). Although these are flexible, they are derived from a half-esterified ester bond due to a polybasic acid anhydride in the main chain, so that the dehydration reaction is caused at a high temperature or the main chain is easily cleaved. In addition, since the carboxyl group is directly bonded to the main chain, the carboxyl group is not sufficient in terms of developability, various coating film resistance, and solder heat resistance.

Further, a photosensitive resin composition containing a phosphorus-based flame retardant is disclosed (Patent Document 5). These systems use a halogen-free flame retardant to reduce the burden on the environment, thereby making it difficult to ignite. However, in order to utilize a halogen-free flame retardant to impart sufficient flame retardancy, it is necessary to add a large amount of a flame retardant, and for this reason, the resolution of the degree of several tens of μm required in recent years is remarkably lowered, and the impedance is made. Since the physical properties other than the flame retardancy required for the agent are lowered, it is not sufficient in terms of both the flame retardancy and the physical properties other than the physical properties.

As described above, in the prior art, sufficient flexibility, folding endurance, and high precision map required for the protective layer for a flexible printed wiring board are achieved. The resin composition and the cured product of all the physical properties, such as the electrical insulating property, the chemical resistance, and the flame retardancy, which are required for the circuit protective layer, are not obtained.

The purpose of the printed wiring board is to improve the size, weight, and communication speed of the portable device. It requires high precision and high density. It is also the same for flexible printed wiring boards that are mainly used in the bending portion of the machine and the periphery of the connecting portion. tendency. From this background, there is an increasing demand for a protective layer for a flexible printed wiring board, and it is necessary to maintain high-precision developability of the resist pattern while maintaining flexibility and folding resistance higher than the prior art. At the same time, it is required to satisfy the properties such as solder heat resistance, substrate adhesion, high insulation, coating resistance, and flame retardancy. The optical solder resists currently on the market are not adequately matched.

[Patent Document 1] Japanese Patent No. 3281473 [Patent Document 2] Japanese Patent No. 2707495 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-279479 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-159815 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-251715

An object of the present invention is to provide a hardened coating film which is excellent in photosensitivity to an active energy ray, can be formed into a fine pattern by development of a dilute alkaline aqueous solution, and is subjected to a post-curing step. Excellent in insulation, adhesion, solder heat resistance, film resistance, flame retardancy, etc., suitable for use in photosensitive resin compositions of optical solder resists and A method for producing a cured product and a photosensitive resin.

In order to solve the above problems, the inventors of the present invention have found that a photosensitive resin composition containing a photosensitive urethane resin (A) having a specific carboxyl group can solve the above problems and complete the present invention.

In other words, the first invention is a photosensitive resin composition containing a carboxyl group-containing photosensitive urethane resin (A), a photopolymerization initiator (B), and a compound containing a photosensitive ethylenically unsaturated group. (C), characterized in that the carboxyl group-containing photosensitive urethane resin (A) is a resin produced by polymer polyol (e) and a carboxylic acid compound having two hydroxyl groups in the molecule ( f) and the diisocyanate compound (g) is reacted as an essential component to form a carboxyl group-containing ethyl urethane prepolymer (a); and the obtained carboxyl group-containing urethane prepolymer (a) a carboxyl group which is reacted with an epoxy group or an oxocyclobutane group in the compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group to form a hydroxyl group-containing ethyl carbamate pre The polymer (c); reacts the hydroxyl group in the obtained hydroxyl group-containing ethyl carbamate prepolymer (c) with the acid anhydride group in the acid anhydride group-containing compound (d).

In the photosensitive resin composition of the first aspect of the invention, the thermosetting compound (D) is further contained.

The photosensitive resin composition of the second aspect of the invention, further comprising a thermosetting auxiliary (E).

Further, the fourth invention is the photosensitive resin group according to any one of the first to third inventions The product wherein the carboxyl group-containing photosensitive urethane resin (A) has an acid value of 10 to 200 mgKOH/g.

The photosensitive resin composition according to any one of the first to fourth aspects of the present invention, wherein the ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin (A) is 200 to 3000 g/ Eq.

The photosensitive resin composition of any one of the first to fifth inventions, wherein the carboxyl group-containing photosensitive urethane resin (A) has a weight average molecular weight of 1,000 to 100,000.

The photosensitive resin composition of any one of the second to sixth inventions, wherein the thermosetting compound (D) is a compound having two or more epoxy groups or oxocyclobutane groups ( k).

Further, the eighth invention is a cured product obtained by curing any one of the photosensitive resin compositions of the first to seventh inventions.

Further, a ninth invention is a photosensitive solder resist ink comprising the photosensitive resin composition of any one of the first to seventh inventions and a flame retardant.

Further, the tenth invention is a dry film type photosensitive solder resist comprising the photosensitive resin composition of any one of the first to seventh inventions and a flame retardant.

Further, the eleventh invention is a method for producing a carboxyl group-containing photosensitive urethane resin, which comprises the first step of bringing a polymer polyol (e) having two hydroxyl groups in a molecule. The carboxylic acid compound (f) and the diisocyanate compound (g) are reacted as an essential component to obtain a carboxyl group-containing ethyl carbamate prepolymer (a); and a second step of the above-mentioned carboxyl group-containing amine group Ethyl formate prepolymerization The compound (a), the epoxy group or the cyclobutane alkyl group is reacted with the ethylenically unsaturated group compound (b) to obtain a hydroxyl group-containing ethyl carbamate prepolymer (c); and the third step And reacting the above-mentioned hydroxyl group-containing ethyl carbamate prepolymer (c) with the acid anhydride group-containing compound (d).

According to the present invention, it is possible to provide an excellent photosensitive property to an active energy ray, a fine pattern can be formed by development of a dilute alkaline aqueous solution, and a cured film obtained by a post-hardening (post-ripening) step is flexible. It is excellent in insulation, adhesion, solder heat resistance, coating film resistance, flame retardancy, etc., and is suitable for a photosensitive resin composition for an optical solder resist, a cured product thereof, and a method for producing a photosensitive resin. The photosensitive resin composition of the present invention can be suitably used as a solder resist for a flexible printed wiring board, a photosensitive cover film, a plating resist, an interlayer electrical insulating material for a wiring board, a photosensitive optical waveguide, or even a pair. A coating layer resist for a flexible printed circuit board on which a conductive paste such as a silver paste or a carbon paste is printed on a film of ethylene phthalate.

The carboxyl group-containing urethane oligomer described in the above Patent Document 4 has a photosensitive resin composition of the present invention containing a half-esterified ester bond due to a polybasic acid anhydride as described above. The characteristic of the substance is that since the main chain does not have the ester bond derived from the half esterification, the main chain is chemically stable, and the various coating films of the obtained hardened coating film are excellent in resistance, even in a high temperature condition such as a solder bath. In other cases, it also exhibits the characteristics of excellent heat resistance. At the same time, it exhibits the unique adhesion and flexibility of the urethane resin. Further, since the carboxyl group-containing photosensitive urethane resin (A) of the present invention has a photosensitive group and a carboxyl group in the side chain, it exhibits excellent developability even when the amount of the carboxyl group is small. Further, in the case where the side chain functional groups are directly bonded to the main chain, excellent photocurability, analytical properties, and coating film resistance can be exhibited due to the rich reactivity. Hereinafter, the photosensitive resin composition of the present invention will be described in detail.

First, the carboxyl group-containing photosensitive urethane resin (A) of the present invention will be described. The carboxyl group-containing photosensitive urethane resin (A) of the present invention is preferably one having an epoxy group or a carboxyl group in the carboxyl group-containing ethyl carbamate prepolymer (a). The ratio of the epoxy group or the oxocyclobutane group in the compound (b) of the oxocyclobutane group to the ethylenically unsaturated group of 0.1 mol to 1.0 mol (more preferably 0.30 mol to 0.95 mol) The reaction is carried out to prepare a hydroxyl group-containing ethyl urethane prepolymer (c), which is 0.1 mol per hydroxy group in the hydroxyl group-containing urethane prepolymer (c). A ratio of -1.0 moles (more preferably 0.30 moles to 0.95 moles) is obtained by reacting an acid anhydride group in the acid anhydride group-containing compound (d).

Further, the above molar ratio is a reaction molar ratio, and each starting material is used in an amount capable of reacting at the above molar ratio. Therefore, for example, there is a case where the carboxyl group is 1 mol with respect to the "carboxyl-containing urethane prepolymer (a)", and "haves an epoxy group or an oxocyclobutane group and an ethyl group." The epoxy group or oxocyclobutane group in the saturated group compound (b) is in an amount of from 0.1 mol to 1.2 mol, and the above-mentioned "carboxyl group-containing amino acid formic acid B" The ester prepolymer (a)" is reacted with the above "compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group". Further, the description relating to the reaction molar ratio in the present specification is synonymous with the above.

Wherein the epoxy group in the compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group is bonded to the carboxyl group-containing ethyl carbamate prepolymer (a) When the proportion of the reaction of the oxocyclobutane group is less than 0.1 mol, the amount of the unsaturated group in the carboxyl group-containing photosensitive urethane resin (A) finally obtained is small, and the photosensitive resin is used. It is difficult to obtain the desired photosensitivity of the composition.

Further, in the compound (b) which has an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group with respect to the carboxyl group 1 in the carboxyl group-containing ethyl carbamate prepolymer (a), The epoxy or oxocyclobutane is reacted in an amount of more than 1.0 mole.

Further, the ratio of the acid anhydride group in the acid anhydride group-containing compound (d) is less than 0.1 mol with respect to the hydroxyl group 1 mol in the hydroxyl group-containing ethyl carbamate prepolymer (c). In this case, the ratio of the carboxyl group introduced is small, and it is difficult to obtain desired developability with respect to the photosensitive resin composition.

Further, the acid anhydride group in the acid anhydride group-containing compound (d) cannot be reacted in an amount of more than 1.0 mol with respect to the hydroxyl group 1 mol in the above hydroxyl group-containing ethyl carbamate prepolymer (c). .

The carboxyl group-containing ethyl urethane prepolymer (a) is reacted with a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as an essential component. Manufacturing. The hydroxyl group-containing compound (h) can be further suitably used [wherein the above-mentioned "polymer polyol (e)" And "except for the carboxylic acid compound (f) having two hydroxyl groups in the molecule", and one or three or more isocyanate compounds (i) and an amine compound (j) having an isocyanate group in the molecule are desired components.

In the present invention, in the synthesis of the carboxyl group-containing ethyl carbamate prepolymer (a), the ratio of the starting material is reacted to the polymer polyol (e), a carboxyl group having two hydroxyl groups in the molecule. The acid compound (f) and the hydroxyl group-containing compound (h) and the amine compound (j) which are added as the case may be a diisocyanate compound in the case where the total of the hydroxyl group and the amine group contained therein are 1 mol. (g) and the isocyanate group having one or more isocyanate groups in the molecule, and the total isocyanate groups contained in the isocyanate group are preferably reacted at a ratio of from 0.50 mol to 1.00 mol, and from 0.70 mol to 0.95. The molar ratio of the moles is better. In the case where the isocyanate group is less than 0.50 mol, the molecular weight of the carboxyl group-containing ethyl carbamate prepolymer (a) becomes small, and it is difficult to obtain desired coating film resistance and film formability. Further, when the isocyanate group is more than 1.00 mol, the remaining isocyanate groups remain in the system, and in the subsequent reaction step, problems of occurrence of by-products or gelation in the reaction tend to occur.

Further, at this time, the polymer polyol (e), the carboxylic acid compound (f) having two hydroxyl groups in the molecule, and the hydroxyl group-containing compound (h) and the amine compound (j) which are added as the case are finally obtained. The acid value of the carboxyl group-containing ethyl carbamate prepolymer (a) is preferably a carboxylic acid compound (f) having two hydroxyl groups in the molecule at a ratio of 5 to 200 mgKOH/g (more preferably 10~) 180 mg KOH / g).

The polymer polyol (e) used in the present invention has two or more hydroxyl groups. The compound is preferably a compound having a weight average molecular weight converted from polyethylene to 500,000 as measured by gel chromatography (hereinafter also referred to as "GPC"). Further, in the present specification, the weight average molecular weight means a weight average molecular weight converted into polyethylene as measured by GPC, within a range not specifically limited. In the present invention, examples of the polymer polyol (e) include polyethylene oxide, polypropylene oxide, ethylene oxide/propylene oxide block copolymer or random copolymer, and polycondensation. a polyether polyol such as a block copolymer of tetramethylene glycol, tetramethylene glycol and neopentyl glycol or a random copolymer; belonging to a polyol or a polyether polyol and maleic anhydride Polyester polyols of condensates of maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid and the like; polyhydric alcohols or bisphenols and carbonates The reaction, or a polycarbonate polyol obtainable by reacting phosgene with a glycol or a bisphenol in the presence of a base; a caprolactone modified polytetramethylene polyol or the like The caprolactone is a polyol such as a polybutadiene-based polyol such as a polyhydric alcohol, a polyolefin-based polyol or a hydrogenated polybutadiene polyol, or an anthrone-based polyol. In the present invention, the polymer polyols (e) may be used singly or in combination of plural kinds.

Among them, polyether polyols such as polytetramethylene glycol, tetramethylene glycol, and neopentyl glycol block copolymers or random copolymers are soft, hydrolyzable, and hydrophilic due to the skeleton. It is excellent in the properties of the coating film, and is particularly preferable because it is excellent in flexibility, chemical resistance, developability, and the like.

The "carboxylic acid compound (f) having two hydroxyl groups in the molecule" used in the present invention has two hydroxyl groups and one or more (preferably one to three) molecules. The compound of a carboxyl group, preferably a compound having a weight average molecular weight of from 90 to 1,000, and examples thereof include dimethylol butyric acid, dimethylolpropionic acid, and the like (caprolactone adduct, ethylene oxide). An adduct, a propylene oxide adduct or the like), 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4-cyclohexanedimethanol or the like.

Among them, dimethylolbutanoic acid and dimethylolpropionic acid are preferred in view of the fact that the concentration of the carboxyl group in the resin can be increased. Further, the caprolactone adduct, the ethylene oxide adduct, the propylene oxide adduct, etc. are capable of reducing the urethane in the carboxyl group-containing ethyl carbamate prepolymer (a). The amount of bonding is used, so it can be used for the purpose of improving the softness of the coating film. Further, an aromatic compound such as hydroxysalicylic acid can be used for the purpose of improving the heat resistance of the coating film.

As described above, in the present invention, the carboxylic acid compound (f) may be appropriately selected depending on the purpose or use, and may be used singly or in combination of plural kinds.

The diisocyanate compound (g) used in the present invention may, for example, be an aromatic diisocyanate having 4 to 50 carbon atoms, an aliphatic diisocyanate, an aromatic aliphatic diisocyanate or an alicyclic diisocyanate.

Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4'-diphenyl group. Methane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3, 5-triisocyanate benzene, dimethoxyaniline diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, and the like.

Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propyl propyl diisocyanate, and 2, 3-tert-butyl diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Examples of the aromatic aliphatic diisocyanate include ω,ω′-diisocyanate-1,3-dimethylbenzene, ω,ω′-diisocyanate-1,4-dimethylbenzene, and ω,ω′. - Diisocyanate - 1,4-diethylbenzene, 1,4-tetramethylbenzenedimethyl diisocyanate, 1,3-tetramethylbenzenedimethyl diisocyanate, etc.

Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [alias: isophorone diisocyanate], 1,3-cyclopentane diisocyanate , 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4 '-Methylene bis(cyclohexyl isocyanate), 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, and the like.

In the present invention, in order to improve the heat resistance of the intended photosensitive resin composition, it is preferred to use an aromatic diisocyanate or an aromatic aliphatic diisocyanate to improve the flexibility of the intended photosensitive resin composition. In the case of using an aliphatic diisocyanate or an alicyclic diisocyanate, it is preferred. In the present invention, the diisocyanate compound (g) may be appropriately selected depending on the purpose or use, and only one type may be used alone. Yes, you can use a variety of types.

The hydroxyl group-containing compound (h) used in the present invention is a compound having one or more hydroxyl groups, and is a compound of the above-mentioned "polymer polyol (e)" and the above "carboxylic acid compound having two hydroxyl groups in the molecule (f) The compound other than the compound of the present invention is exemplified by a monoalcohol compound (h1) having one hydroxyl group in the molecule; having two hydroxyl groups in the molecule, having no carboxyl group, and having a weight average molecular weight of 50 a diol compound (h2) of ~499; a polyol compound (h3) having 3 or more hydroxyl groups in the molecule and having a weight average molecular weight of 50 to 499. These may also have a functional group other than a hydroxyl group and a hydroxyl group in the molecule. Further, it may be used alone or in combination of plural kinds.

Examples of the monool compound (h1) having one hydroxyl group in the molecule include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, and lauryl alcohol. An aliphatic monoalcohol such as stearic acid alcohol; an alicyclic monoalcohol such as cyclohexanol; an aromatic monool such as benzyl alcohol, decyl alcohol, phenol or methoxyketone; and a single functional group other than a hydroxyl group An alcohol compound having a hydroxyl group-containing carboxylic acid compound such as 12-hydroxystearic acid or 2-hydroxyethyl (meth) acrylate (combined "2-hydroxyethyl acrylate" and "2-hydroxyethyl methacrylic acid" The ester is described as "2-hydroxyethyl (meth) acrylate", the same applies hereinafter), a hydroxyl group-containing (meth) acrylate compound such as 4-hydroxybutyl (meth) acrylate, or glycidol ( A hydroxyl group-containing epoxy compound such as glycidol) or a hydroxyl group-containing oxocyclobutane compound such as oxocyclobutanol.

Others, single-end oxidized polyethylene glycol, single-end methoxy An oligomeric monoalcohol such as a polypropylene glycol or a caprolactone adduct starting from a monool.

In the present invention, in the case of using the monool compound, since the polymerization terminal of the obtained carboxyl group-containing ethyl carbamate prepolymer (a) can be blocked, it is intended to synthesize a low molecular weight carboxyl group-containing amine group. When the ethyl formate prepolymer (a) is used, etc., it can be suitably used when adjustment of a molecular weight is required. Further, in the case of using a hydroxyl group-containing compound having a functional group other than a hydroxyl group, since a functional group other than a hydroxyl group can be introduced to the terminal of the carboxyl group-containing ethyl carbamate prepolymer (a), it is required The terminal modification of the carboxyl group-containing urethane prepolymer (a) can be suitably employed. In the present invention, in consideration of reactivity of a hydroxyl group or polymerization control, use of lauryl alcohol, stearic acid alcohol, cyclohexanol, 12-hydroxystearic acid, glycidol, 2-hydroxyethyl (methyl) Acrylate, 4-hydroxybutyl (meth) acrylate, etc. are preferred.

Examples of the diol compound (h2) having two hydroxyl groups in the molecule and having no carboxyl group and having a weight average molecular weight of 50 to 499 include ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , propylene glycol, dipropylene glycol, butanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl An aliphatic diol such as an alcohol, 1,9-nonanediol, hydrogenated bisphenol A, 1,4-cyclohexanedimethanol, or spiro-glycol; hydroxyketone, 1,3-dihydroxybenzene , 1,2-dihydroxybenzene, bisphenol, bisphenoxyethanol oxime, bisphenol oxime, biscresol oxime and other aromatic diols; N,N-bis(2-hydroxypropyl)aniline, N, N-bis(2-hydroxyethyl)aniline, N,N-bis(2-hydroxyethyl)methylamine, N,N-bis(2-hydroxyethyl)propyl Amine, N,N-bis(2-hydroxyethyl)butylamine, N,N-bis(2-hydroxyethyl)hexylamine, N,N-bis(2-hydroxyethyl)octylamine, N a diol compound having a 3-stage amine group such as N-bis(2-hydroxyethyl)benzylamine or N,N-bis(2-hydroxyethyl)cyclohexylamine; and others may include a diol having a sulfur atom , a diol containing a bromine atom, and the like. In the present invention, the diol compound (h2) may be used alone or in combination of plural kinds. In the present invention, by using a diol compound having a tertiary amino group such as N,N-bis(2-hydroxypropyl)aniline, since the cohesive force of the coating film is large, resistance can be formed while maintaining flexibility. Excellent and strong coating film, so it is better.

The polyol compound (h3) having three or more hydroxyl groups in the molecule and having a weight average molecular weight of 50 to 499 may, for example, be trimethylolethane, polytrimethylolethane or trimethylolpropane. , polytrimethylolpropane, pentaerythritol, polypentaerythritol, Pearitol, mannitol, arabitol, xylitol, galactitol, glycerol, and the like. In the present invention, in the case of using the polyol compound (h3), since a part of the obtained carboxyl group-containing ethyl carbamate prepolymer (a) can be branched, the cured product is The crosslink density increases, and the resistance of the hardened coating film can be improved. Therefore, in the present invention, it is also possible to use it as needed for the purpose of improving the durability of the cured coating film. Among the polyol compounds (h3), trimethylolpropane or pentaerythritol is preferably used in terms of reaction control.

The "isocyanate compound (i) having one or three or more isocyanate groups in the molecule" used in the present invention, specifically, one molecule Examples of the monofunctional isocyanate having one isocyanate group include (meth)acryloyloxyethyl isocyanate, 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate, and vinyl isocyanate. Allyl isocyanate, (meth) propylene decyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate, and the like. Further, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, Benzyl diisocyanate, 2,4-diisocyanate, benzene diisocyanate, 2,4-diisocyanate toluene, hexamethylene diisocyanate, diisocyanate 4 -Methyl-m-phenylene ester, stilbene diisocyanate, p-phenylene diisocyanate, tetramethyl dimethyl diisocyanate, cyclohexylmethane diisocyanate, hydrogenated dimethyl diisocyanate, cyclohexyl Isocyanate, tolidine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, m-tetramethylbenzyl diisocyanate a diisocyanate compound such as tetramethyl dimethyl diisocyanate or dimer acid diisocyanate, and a compound which reacts with a vinyl monomer having a hydroxyl group, a carboxyl group or a guanamine group in an amram group may also be regarded as an isocyanate. Used as a compound.

In addition, examples of the polyfunctional isocyanate having three or more isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and isocyanuric acid isocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates. Further, examples thereof include a trimethylolpropane adduct of the above diisocyanate (g), a burette body which reacts with water, and a trimer having an isomeric cyanate ring.

In the present invention, in order to reduce the prepolymerization of ethyl carbamate containing a carboxyl group When the unreacted hydroxyl group remaining at the end of the substance (a) is used for the purpose of blocking the terminal, it is preferred to use a monofunctional isocyanate having one isocyanate group in one molecule, and to enhance the transmission light hardening by the photosensitive method of the present invention. The coating film obtained by the resin composition, or the resistance of the coating film obtained by photohardening and thermosetting, etc., and the branching of the urethane-containing prepolymer (a) having a carboxyl group Among them, a polyfunctional isocyanate having three or more isocyanate groups in one molecule is preferably used. In the present invention, the isocyanate compounds may be appropriately selected depending on the purpose or use, and may be used singly or in combination of plural kinds.

Further, in the present invention, when the carboxyl group-containing ethyl carbamate prepolymer (a) is synthesized, the amine compound (j) can be reacted as a desired component. The amine compound (j) in the present invention means a compound having at least one primary or secondary amine group in the molecule.

The amine compound (j) of the present invention may, for example, be a monoamine compound such as propylamine, hexylamine, cyclohexylamine, benzylamine, 2-ethylhexylamine, octylamine, dodecylamine or aniline; ethylenediamine , propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, tris-ethyltetramine, diethylenetriamine, triaminepropane, 2,2,4-trimethylhexamethylenediamine, methylphenylene diamine, anthracene, piperazine Aliphatic polyamines; alicyclic polyamines such as isophorone diamine, dicyclohexylmethane-4,4'-diamine; and aromatic polyamines such as phenyldiamine and phenyldimethyldiamine .

Further, a diamine compound such as a two-terminal amine-modified polyoxyethylene, a two-terminal amine-modified polyoxypropylene, a polyfluorenone diamine, or a polybutadiene diamine; or a single-end amine-based modification may be mentioned. Polyoxyethylene, single-end amine modified polyoxypropylene A monoamine compound such as an alkene, a polyfluorene monoamine or a polybutadiene monoamine; or a polymeric polyamine compound such as an ethylenimine or a polyallylamine.

Further, as the amine compound (j), a (meth) acrylate group of a compound having a first-order amine and a (meth) acrylate group containing a (meth) acrylate group may be subjected to a Michael addition reaction. (Michael reaction), an amine compound obtained by upgrading to a 2-stage amine group. In the case of using such a compound, a (meth) acrylate group-containing compound can be worked on, whereby a polar functional group is introduced into the carboxyl group-containing urethane prepolymer (a). For example, an acrylate group of 4-hydroxybutyl acrylate is subjected to methic acid addition to the amine group of the isophorone diamine, a diamine having a quaternary amine group is synthesized, and an amine as the present invention is used. A raw material of a urethane resin, whereby a hydroxyl group can be introduced into the resin.

Further, as the amine compound (j) of the present invention, an amine compound having a functional group other than an amine group can also be used. For example, 2-hydroxyethyl-extended ethyldiamine, N-(2-hydroxyethyl)-propylidenediamine, (2-hydroxyethyl-propyl)diamine, (di- 2-hydroxyethyl-ethyl) a diamine having a hydroxyl group such as diamine, (di-2-hydroxyethylpropyl)diamine, (2-hydroxypropylexeneethyl)diamine, (di-2-hydroxypropylexeneethyl)diamine a dimer acid diamine which converts a carboxyl group of a dimer acid into an amine group, and a polyoxyalkylene diethylene glycol diamine which has a propoxyamino group at both terminals.

In the present invention, the amine compound (j) may be used singly or in combination of a plurality of kinds, and a monoamine, a diamine or a polyamine may be appropriately selected depending on the purpose or use.

For example, in the synthesis of a metal urethane prepolymer containing a carboxyl group (a) Further, by using a monoamine compound in combination, the molecular weight can be easily controlled because the amount of residual isocyanate can be reduced and the terminal can be blocked. Further, by using a diamine compound, it is possible to obtain an elongated polymer chain, and a polymer having a high molecular weight can be obtained. Even by using a polyamine compound, the polymer chain can be branched, and finally the cohesive force and resistance of the coating film can be improved.

The method of reacting the amine compound (j) may be carried out by simultaneously adding another raw material such as the polymer polyol (e) to the diisocyanate compound (g) [and, if appropriate, further to the isocyanate compound (i). The method of carrying out the reaction; or synthesizing the amino acid chain of the isocyanate terminal in advance, and performing chain extension by dropping or adding the amine compound (j), thereby obtaining a carboxyl group-containing amine having a urea bond A method of prepolymer (a) of ethyl carbamate or the like. In the present invention, in the case where the amine compound (j) is reacted in this manner, the cohesive force of the obtained carboxyl group-containing photosensitive urethane resin (A) can be enhanced, and heat resistance and durability are further improved. The film is applied, so the amine compound (j) may be used as needed.

In the present invention, the synthesis conditions of the carboxyl group-containing ethyl carbamate prepolymer (a) are not particularly limited, and can be carried out under known conditions.

For example, a polymer polyol (e), a carboxylic acid compound (f), and a solvent [and a hydroxyl group-containing compound (h) according to the case] are added to a flask, and heated under a nitrogen gas flow in a range of 20 to 120 °C. ‧ stirring, uniformly dissolving, adding diisocyanate compound (g) [and, according to the case, isocyanate compound (i)], heating at 50 to 150 ° C while stirring, can be obtained by preliminarily obtaining ethyl carbamate containing carboxyl group Polymer (a). In this case, an organotin compound, a compound containing a tertiary amine group, or the like may be used as needed. A urethane catalyzed catalyst.

Further, before the addition of the diisocyanate compound (g), the polymer polyol (e), the carboxylic acid compound (f), and the solvent added to the flask may be heated and stirred at 100 ° C or higher in advance. One part of the solvent is desolvated. This operation is usually carried out in order to remove moisture (dehydration treatment) in the system, and by this operation, when the diisocyanate compound (g) is reacted, the isocyanate group deactivation due to water can be suppressed, and finally A carboxyl group-containing ethyl carbamate prepolymer (a) having a physical property value closer to the theoretical value is obtained.

Next, in the present invention, a carboxyl group-containing ethyl carbamate prepolymer (a) is reacted with a compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group to synthesize a hydroxyl group. The ethyl urethane prepolymer (c).

In the present invention, as a ratio of reacting a carboxyl group-containing ethyl carbamate prepolymer (a) with a compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group, As shown in the above description, it is preferred to have an epoxy group or an oxocyclobutane group and an ethylenic unsaturated group with respect to the carboxyl group 1 mole in the carboxyl group-containing ethyl carbamate prepolymer (a). The epoxy group or oxocyclobutane group in the compound (b) is reacted in a ratio of from 0.1 mol to 1.0 mol (more preferably from 0.3 mol to 0.95 mol).

Here, the epoxy in the compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group with respect to the carboxyl group in the carboxyl group-containing ethyl carbamate prepolymer (a) If the ratio of the reaction of the group or the oxocyclobutane group is less than 0.1 mol, the photosensitive tree containing the carboxyl group finally obtained Since the amount of the unsaturated group in the lipid composition (A) is small, it is difficult to obtain the desired photosensitivity in the photosensitive resin composition.

The "compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group" used in the present invention is preferably a compound having a carbon number of 6 to 50, and examples thereof include a glycidyl group (A) Acrylate, glycidyl cinnamic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl ( Methyl) acrylate, (3,4-epoxycyclohexyl)methyl (meth) acrylate, 4-vinyl-1-cyclohexane-1,2-epoxy compound, 1,3-butyl Ethyl monoepoxide, oxocyclobutyl (meth) acrylate, oxocyclobutyl cinnamic acid or pentaerythritol triacrylate, such as epichlorohydrin, a polyfunctional acrylate-based monomer containing a hydroxyl group a polyfunctional acrylate group-containing monoepoxide for reacting on a hydroxyl group; or an average of one molecule obtained by modifying a large semi-epoxy group of a phenol novolak type epoxy resin to an acrylate group by using acrylic acid or the like a monoepoxide containing a polyfunctional acrylate group having one epoxy group remaining; a ring of a compound having two or more epoxy groups in the molecule A polyfunctional acrylate-based monoepoxide or the like obtained by reacting a part of a group with a carboxyl group of a polyfunctional acryl-based monomer having a carboxyl group, by using the epoxy group or oxocyclobutane group By reacting with a carboxyl group in the ethyl urethane prepolymer (a), a hydroxyl group-containing ethyl urethane prepolymer (c) can be obtained. In the present invention, the compound (b) having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group may be used singly or in combination of plural kinds.

Among them, in the present invention, due to the pretreatment with ethyl carbamate containing a carboxyl group The reactivity of the carboxyl group in the polymer (a) is sufficient, and the photosensitive resin composition obtained is excellent in photosensitivity, so glycidyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate is used. Ester glycidyl ether and the like are particularly preferred.

Further, in the present invention, "the compound (o) having no ethylenic unsaturated group and having an epoxy group or an oxocyclobutane group" and "having an epoxy group or an oxocyclobutane group" may be used in combination. Compound (b) with an ethylenically unsaturated group. The compound (o) having no ethylenically unsaturated group and having an epoxy group or an oxocyclobutane group, which is used in the present invention, is preferably a compound having 6 to 50 carbon atoms, and for example, : styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamate, methyl glycidyl ether, butyl glycidyl Ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearic acid glycidyl ether, allyl glycidyl ether, glycidol, N-glycidyl sulfoxide An amine, 1,3-dibromophenyl glycidyl ether, CELLOXIDE 2000 (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), oxocyclobutanol or the like.

In the present invention, the "compound (o) having no ethylenically unsaturated group and having an epoxy group or an oxocyclobutane group" is the same as "having an epoxy group or an oxocyclobutane group" The compound (b) of the ethylenically unsaturated group is used in combination, and the photosensitivity of the carboxyl group-containing photosensitive urethane resin (A) of the present invention can be widely controlled. Therefore, it is preferred to use it appropriately for the purpose or use.

a carboxyl group in a carboxyl group-containing ethyl carbamate prepolymer (a) and a compound having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group (b) The reaction conditions in the case where the epoxy group or the oxocyclobutane group is reacted are not particularly limited, and can be carried out under known conditions. For example, a carboxyl group-containing ethyl carbamate prepolymer (a), a compound having an epoxy group or an oxocyclobutane group and an ethylenically unsaturated group (b) [and, as the case may be, no ethylenic property" a compound containing an epoxy group or an oxocyclobutane group (o)"] and a solvent are added to a flask, and heated at 50 to 150 ° C while stirring under a flow of oxygen, a hydroxyl group-containing amine can be obtained. Ethyl carbamate prepolymer (c). In this case, it is preferred to add a compound having a tertiary amino group such as triethylamine or dimethylbenzylamine as a catalyst, or to add ethylene such as hydroquinone or methoquinone. Polymerization inhibitors for unsaturated groups. The amount of the catalyst added is preferably 0.1 to 10% by weight based on the total of (a) and (b), and the amount of the inhibitor is added in the range of 0.05 to 10% by weight.

Further, in the present invention, in the production of the photosensitive urethane resin (A) having a carboxyl group, the hydroxyl group-containing ethyl carbamate prepolymer (c) and the acid anhydride group-containing compound (d) are used. The reaction is characterized by it. The acid anhydride group-containing compound (d) used in the present invention is a compound having an acid anhydride group, and can be obtained by reacting an acid anhydride group thereof with a hydroxyl group in a hydroxyl group-containing ethyl carbamate prepolymer (c). The photosensitive urethane resin (A) containing a carboxyl group of the present invention.

In the present invention, the ratio of reacting the hydroxyl group-containing ethyl carbamate prepolymer (c) with the acid anhydride group-containing compound (d) is relative to the above hydroxyl group-containing ethyl carbamate prepolymer (c) An acid anhydride group in the acid anhydride group-containing compound (d) at a ratio of 0.1 mole to 1.0 mole Carry out the reaction.

Referring to the hydroxyl group 1 mole in the hydroxyl group-containing ethyl carbamate prepolymer (c), if the ratio of the acid anhydride group in the acid anhydride group-containing compound (d) is less than 0.1 mol, the introduction is carried out. The ratio of the hydroxyl group having excellent curability and developability is small, and it is difficult to obtain desired developability.

The acid anhydride group-containing compound (d) used in the present invention is preferably a compound having one or two carboxylic anhydride groups in the molecule and having a carbon number of 4 to 50, and examples thereof include phthalic anhydride and trimellitic anhydride. Methyltetrahydrophthalic anhydride, methyl-3,6-terminal methylidene-1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, A An alicyclic structure or an aromatic ring, such as pentahydrophthalic anhydride, methyl trihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, HET acid (chlrendic acid anhydride, tetrabromophthalic anhydride) An anhydride-containing compound is constructed. Examples of the other acid anhydride group-containing compound (d) include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, and dodecyl succinic anhydride. Butyl maleic anhydride, heptyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, mercapto maleic anhydride, dodecyl maleic anhydride, butyl branamide Anhydride, hexyl branamine anhydride, heptyl branamine anhydride, octyl branamine anhydride, decyl branamine anhydride, dodecyl glutamine anhydride, and the like. In the present invention, the acid anhydride group-containing compound (d) may be used singly or in combination of plural kinds.

Among them, succinic anhydride, tetrahydrofurfuric anhydride, and the like are excellent in developability, pattern formability, and coating film resistance of the photosensitive resin composition obtained in the present invention. Often superior, so especially good.

The reaction conditions at the time of reacting the hydroxyl group in the hydroxyl group-containing ethyl carbamate prepolymer (c) with the acid anhydride group of the acid anhydride group-containing compound (d) are not particularly limited, and can be carried out under known conditions. For example, a hydroxyl group-containing ethyl carbamate prepolymer (c) and an acid anhydride group-containing compound (d) and a solvent are added to a flask, and heated at 50 to 150 ° C while stirring under a flow of oxygen. A photosensitive urethane resin (A) having a carboxyl group is obtained. In this case, it is preferred to add a compound having a tertiary amino group such as triethylamine or dimethylbenzylamine as a catalyst, in which case, prepolymerization is carried out with respect to the hydroxyl group-containing ethyl carbamate. The total of the compound (c) and the acid anhydride group-containing compound (d) is preferably added in the range of 0.1 to 10% by weight.

The acid value of the carboxyl group-containing photosensitive urethane resin (A) of the present invention is preferably from 10 to 200 mgKOH/g, particularly preferably from 30 to 150 mgKOH/g. When the acid value is less than 10 mgKOH/g, it is difficult to obtain sufficient developability. For example, in the portion where the film is to be dissolved and removed during development, the film remains as a residue. In addition, when the acid value is more than 200 mgKOH/g, the solubility of the coating film with respect to the developer becomes high, and the portion which is desired to remain as a pattern is also photohardened, resulting in a poor pattern shape.

The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin (A) of the present invention is preferably 200 to 3000 g/eq, more preferably 300 to 2000 g/eq. When the equivalent of the ethylenically unsaturated group is less than 200 g/eq, the photosensitivity is too high, and the portion to be removed by the dissolution of the film during development is also photohardened, and a good pattern shape cannot be obtained. When B When the equivalent of the ethylenically unsaturated group exceeds 3,000 g/eq, the light sensitivity is too low, and the portion to be photohardened cannot be sufficiently cured, and the pattern is dissolved during development, and a good pattern shape cannot be obtained.

In addition, the "equivalent of the ethylenically unsaturated group" in the present invention means the theoretical value calculated from the weight of the raw material used in the synthesis of the resin, and the weight of the resin is divided by the amount of the ethylenically unsaturated group present in the resin. It is equivalent to the weight of the resin per 1 mol of ethylenically unsaturated group, that is, the reciprocal of the ethylenically unsaturated group concentration.

The weight average molecular weight of the carboxyl group-containing photosensitive urethane resin (A) of the present invention is preferably from 1,000 to 100,000, more preferably from 3,000 to 60,000. When the weight average molecular weight is less than 1,000, there is a possibility that sufficient solder heat resistance and flexibility are not obtained. In addition, when the weight average molecular weight exceeds 100,000, the solder heat resistance is excellent, but the developability may be deteriorated, and there is also a problem of viscosity and handleability at the time of coating.

The photosensitive urethane resin containing a carboxyl group (A) according to the production method of the present invention comprises the first step of polymer polyol (e), a carboxylic acid compound having two hydroxyl groups in the molecule ( f), the diisocyanate compound (g) is reacted as an essential component to obtain a carboxyl group-containing ethyl carbamate prepolymer (a); and the second step is to obtain a carboxyl group obtained in the first step The ethyl urethane prepolymer (a), the epoxy group or the oxocyclobutane group and the ethylenically unsaturated group compound (b) are reacted to obtain a hydroxyl group-containing ethyl carbamate prepolymerization. And (c); and a third step of the hydroxyl group-containing amino carboxylic acid B obtained in the second step The ester prepolymer (c) is reacted with the acid anhydride group-containing compound (d).

The reaction conditions in the first step are preferably carried out by heating and stirring at a temperature of from room temperature to 180 ° C., and a reaction catalyst may be used as needed. The reaction conditions in the second step are preferably carried out by heating and stirring at a temperature of 50 to 150 ° C in the presence of oxygen, and a polymerization inhibitor and a polymerization inhibitor of an ethylenically unsaturated group may be used as needed. Further, as the reaction condition of the third step, in the same manner as the second step, the reaction is preferably carried out by heating and stirring at 50 to 150 ° C in the presence of oxygen, and after the second step, a new reaction can be added as needed. A polymerization inhibitor for vehicles and ethylenically unsaturated groups.

Further, when the carboxyl group-containing ethyl carbamate prepolymer (a) is produced in the first step, the polymer polyol (e), the carboxylic acid compound (f) having two hydroxyl groups in the molecule, and the diisocyanate are obtained. The compound (g) is reacted as an essential component, and may be further reacted with the above-described hydroxyl group-containing compound (h) as an optional component, the above-mentioned isocyanate compound (i) as an optional component, and the above-mentioned amine compound (j) as an optional component. .

Further, the solvent used in the synthesis of the above-mentioned carboxyl group-containing photosensitive urethane resin (A) can be appropriately selected depending on the end use or the solubility of the reactant. For example, in the case where the end use is a dry film type photosensitive solder resist, in the dry film forming step, since it is necessary to rapidly dry the solvent, it is preferred to use a low boiling point solvent. Examples of the low boiling point solvent in this case include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, and isopropyl alcohol. Also, in the case where the final use is a liquid solder resist, in the ink manufacturing step, when considering the filling When a material or a pigment is kneaded by a drum or as a storage stability of an ink, it is preferable to use a high boiling point solvent because it is necessary to suppress the volatilization of the solvent as much as possible. Examples of the high boiling point solvent in this case include carbitol acetate, methoxypropyl acetate, cyclohexanone, and diisobutyl ketone.

In the present invention, these solvents may be used singly or in combination of plural kinds as needed. Further, solvent removal may be carried out during the reaction, or after the solvent is removed, another new solvent may be added.

The photosensitive resin composition of the present invention comprises a photosensitive urethane resin (A) containing a carboxyl group, a photopolymerization initiator (B), and a photosensitive ethylenically unsaturated compound (C).

The photopolymerization initiator (B) is added for the purpose of curing an active energy ray (for example, ultraviolet light to cure a photosensitive compound. As a photopolymerization initiator, if it has a function of starting ethylene polymerization by photoexcitation) The monocarbonyl compound, the dicarbonyl compound, the acetophenone compound, the benzoin ether compound, the decylphosphine oxide compound, the amine carbonyl compound, or the like can be used.

Specific examples of the monocarbonyl compound include diphenyl ketone, 4-methyl-diphenyl ketone, 2,4,6-trimethyldiphenyl ketone, and methyl phthalyl phenyl benzene. Formate, 4-phenyldiphenyl ketone, 4-(4-methylphenylthio)phenyl-toluene, 3,3'-dimethyl-4-methoxydiphenyl ketone, 4- (1,3-propenylmercapto-1,4,7,10,13-pentaoxytridecyl)diphenyl ketone, 3,3',4,4'-tetra(t-butylperoxy) Dicarbonyl ketone, 4-benzylidene-N,N,N-trimethylbenzylammonium chloride, 2-hydroxy-3-(4-benzylidene-phenoxy)- N,N,N-trimethyl-1-propanamine hydrochloride, 4-benzylidene-N,N-dimethyl-n-[2-(1-o-oxy-2-propenyloxy) Base ethyl)]methylammonium bromide, 2-/4-isopropyl 9-oxosulfur (thioxanthone), 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 1-chloro-4-propoxy 9-oxosulfur 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-oxygen sulphide -2-thyroxine)-N,N,N-trimethyl-1-propanamine hydrochloride, benzhydrylmethylene-3-methylnaphthalene (1,2-d)thiazoline (thiazoline, C ₃ H ₅ NS) and the like.

Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo[2.1.1]heptane-2,3-dione, diphenylethylenedione, 2-ethyl onion, and 9 , 10-phenanthrenequinone, methyl-α-oxyphenylacetate, 4-phenyldiphenylethylenedione, and the like.

Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-(4-isopropylphenyl)2-hydroxy-2-methyl-1. -Phenylpropan-1-one, 1-(4-isopropylphenyl)2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl Ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymer, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1 ,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylsulfide Phenyl]-2- Tropicpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Lolinyl-phenyl)butan-1-one, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)anthracene, 3,6-bis(2-methyl-2- Orolinyl-acetonyl)-9-butylcarbazole and the like.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-propyl. Ether and the like.

Examples of the cerium oxide phosphine compound include 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and 4-n-propylphenyl-bis(2,6-dichlorobenzamide). Phosphine oxide and the like.

Examples of the aminocarbonyl compound include methyl-4-(dimethylamino)benzoate, ethyl-4-(dimethylamino)benzoate, and 2-n-butoxy group. Ethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-(dimethylamino)ethyl benzoate , 4,4'-bis-4-dimethylaminodiphenyl ketone, 4,4'-bis-4-diethylaminodiphenyl ketone, 2,5'-bis-(4-di Ethylaminobenzylidene)cyclopentanone and the like.

Wherein, in the present invention, in combination 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one and 9-oxosulfur In the case of use, it is particularly preferable because it is inexpensive and excellent in photosensitivity.

These are not limited to the above-mentioned compounds, and may be any one having the ability to initiate polymerization by permeating active energy rays. These may be used singly or in combination, and the amount used is not limited, and it is preferably added in an amount of from 1 to 20 parts by weight based on 100 parts by weight of the total dry weight of the carboxyl group-containing photosensitive urethane resin (A). . Further, a known organic amine may be added as a sensitizer.

Next, the photosensitive ethylenically unsaturated group-containing compound (C) of the present invention will be described. The compound (C) is usually blended with a general photosensitive compound such as a photosensitive solder resist ink, and has an ethylenically unsaturated double bond in its structure. In the present invention, a photosensitive compound not limited to the above-mentioned "carboxyl group-containing photosensitive urethane resin (A)" can be used as a photosensitive ethylenic group in the above-mentioned general photosensitive compound. Unsaturated group Compound (C). The photosensitive ethylenically unsaturated group-containing compound (C) which can be used in the present invention has an ethylenically unsaturated double bond in the structure and is not contained in the above-mentioned "carboxyl group-containing urethane resin (A). The above-mentioned limitation is not particularly limited, and examples thereof include an alkyl-based (meth)acrylate, an alkylglycol-based (meth)acrylate, and a compound having a carboxyl group and an ethylenically unsaturated group. The compound contained in the definition of the carboxyl group-containing urethane resin (A), the (meth) acrylate compound having a hydroxyl group, the nitrogen-containing (meth) acrylate compound, and the like are not included. Further, a monofunctional or polyfunctional compound can be suitably used. In terms of photocurability and hard coatability of the coating film, it is preferred to be a polyfunctional one.

More specifically, the alkyl (meth) acrylate is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, or butyl (methyl). Acrylate, pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate , mercapto (meth) acrylate, mercapto (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate Ester, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, cetyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, icosyl (meth) acrylate, behenyl (methyl) An alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms, such as an acrylate, preferably has a carbon number of 2 to 10 (more preferably a carbon number) for the purpose of adjusting polarity. 2~8) alkyl group (methyl) C Oleate.

Further, examples of the alkyl glycol type (meth) acrylate include diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tetraethylene glycol mono( Methyl) acrylate, hexaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, Tetrapropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, etc.; mono(meth) acrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain; methoxy Ethylene glycol (meth) acrylate, methoxy diethylene glycol (meth) acrylate, methoxy triethylene glycol (meth) acrylate, methoxytetraethylene glycol (methyl) Acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) acrylate, n-pentyloxy Tetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (A Acrylate, ethoxytetrapropylene glycol (meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentyloxytetrapropylene glycol (methyl) Acrylate, polytetramethylene glycol (meth) acrylate, methoxy polytetramethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, B An oxypolyethylene glycol (meth) acrylate, a mono(meth) acrylate having an alkoxy group at the terminal and having a polyoxyalkylene chain; phenoxy diethylene glycol (meth) acrylate, Phenoxyethylene glycol (methyl) Acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxy hexaethylene glycol (meth) acrylate, phenoxy polyethyl acrylate The diol (meth) acrylate and phenoxytetrapropylene diol (meth) acrylate are equal to polyoxyalkylene (meth) acrylate having a phenoxy group or an aryloxy group at the terminal.

Further, as a compound having a carboxyl group and an ethylenically unsaturated group other than the carboxyl group-containing urethane resin (A), for example, maleic acid, fumaric acid, itaconic acid, and kumquat can be exemplified. Acid or such alkyl or alkenyl monoester, β-(meth)acryloxyethyl monoester, β-(meth)acryloxyethyl monoester isophthalate And β-(meth)acryloyloxyethyl monoester terephthalate, β-(meth)acryloxyethylethyl succinate, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and the like.

Further, examples of the compound having a hydroxyl group and an ethylenically unsaturated group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (methyl). ) acrylate, glycerin mono (meth) acrylate, 4-hydroxyvinyl benzene, and the like.

Further, examples of the compound having a nitrogen atom and an ethylenically unsaturated group include (meth)acrylic acid decylamine, N-methylol (meth)acrylic acid decylamine, and N-methoxymethyl group. -(Meth)acrylamide, N-ethoxymethyl-(meth)acrylamide, N-propoxymethyl-(meth)acrylamide, N-butoxy Mono-hydroxyalkyl (meth) decylamine such as benzyl-(meth)acrylamide or N-pentyloxymethyl-(meth)acrylamide; N,N-di(hydroxymethyl) Acrylic decylamine, N-methylol-N-methoxymethyl (meth) decyl decylamine, N,N-bis(methoxymethyl) decyl decylamine, N-ethoxyl Methyl-N-methoxymethyl methacrylate decylamine, N,N-bis(ethoxymethyl) decyl decylamine, N-ethoxymethyl-N-propoxymethyl group Acrylate decylamine, N,N-bis(propoxymethyl) decyl decylamine, N-butoxymethyl-N-(propyloxymethyl) methacrylate decylamine, N, N -Bis(butoxymethyl)acrylamide, N-butoxymethyl-N-(methoxymethyl)methacrylamide, N,N-bis(pentyloxymethacrylate Base amine An acrylamide-based unsaturated compound such as a dihydroxyalkyl (meth) acrylamide such as N-methoxymethyl-N-(pentyloxymethyl) methacrylate or dimethylamine; dimethylamine Ethyl ethyl (meth) acrylate, diethyl amino ethyl (meth) acrylate, methyl ethyl amide ethyl (meth) acrylate, dimethyl amino styrene, diethyl An unsaturated compound having a dialkylamino group such as an amino styrene; and a halogen ion such as Cl-, Br- or I- as a counter ion or QSO ^3- (Q: an alkyl group having 1 to 12 carbon atoms) A quaternary ammonium salt of a dialkylamino group-containing unsaturated compound.

Further, examples of the other unsaturated compound include perfluoromethylmethyl (meth) acrylate, perfluoroethyl methyl (meth) acrylate, and 2-perfluoro butyl ethyl (methyl). Acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, 2-perfluoroisodecylethyl (meth) acrylate, 2- Perfluorodecylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropyl propyl (meth) acrylate, perfluorooctyl propyl (methyl) a perfluoroalkylalkyl group having a perfluoroalkyl group having 1 to 20 carbon atoms such as acrylate, perfluorooctylpentyl (meth) acrylate or perfluorooctylundecyl (meth) acrylate (meth) acrylates; Perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene, and other perfluoroalkyl-containing vinyl monomers such as perfluoroalkyl groups; vinyl trichlorodecane a vinyl compound containing an alkoxyalkyl group such as vinyl tris(β-methoxyethoxy)decane, vinyl triethoxydecane, γ-(meth)acryloxypropyltrimethoxydecane And derivatives thereof; glycidyl (meth) acrylate, glycidyl group-containing (meth) acrylate such as 3,4-epoxycyclohexyl (meth) acrylate, etc.; One or more types are appropriately selected in the group.

Further, as the fatty acid vinyl compound, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl octanoate, vinyl laurate, vinyl palmitate, vinyl stearate, or the like may be used. As the alkyl vinyl ether compound, butyl vinyl ether, ethyl vinyl ether or the like is also used; as the α-olefin compound, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, etc.; as the vinyl compound, allyl acetate, allyl alcohol, allylbenzene, cyanyl allyl, etc. may also be used. Base compound; vinyl cyanide, vinyl cyclohexane, vinyl methyl ketone, styrene, α-methyl styrene, 2-methyl styrene, chlorostyrene, etc.; as an ethynyl compound, it can also be used Acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol, and the like.

Next, two or more polyfunctional compounds having an ethylenically unsaturated group are specifically exemplified.

First, among the compounds having an ethylenically unsaturated group, an aliphatic compound is exemplified. Specific examples thereof include: 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and new Pentylene glycol di(meth)acrylate, bis(propylene decyloxy neopentyl glycol) adipate, bis(methacryloxy neopentyl glycol) adipate, epichlorohydrin modification 1,6-hexanediol di(meth)acrylate: KAYARAD R-167 manufactured by Nippon Kayaku Co., hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, caprolactone modified hydroxytrimethyl Neopentyl glycol di(meth)acrylate: alkyl (meth) acrylate such as KAYARAD HX series manufactured by Nippon Kayaku Co., ethylene glycol di(meth) acrylate, diethylene glycol di(methyl) Acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, epichlorohydrin modified ethylene glycol II Methyl acrylate: Denacol DA(M)-811, epichlorohydrin-modified diethylene glycol di(meth) acrylate: Denacol DA(M)-851, propylene glycol di(methyl) Acrylate, dipropylene glycol di(meth)acrylate, tripropylene Di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, epichlorohydrin modified propylene glycol di(meth)acrylate: Changchun industry Denacol DA(M) -911 and other alkyl glycol type (meth) acrylate, trimethylolpropane tri (meth) acrylate, di-trimethylolpropane tri (meth) acrylate, neopentyl glycol modification Trimethylolpropane di(meth)acrylate: KAYARAD R-604, manufactured by Nippon Kayaku Co., Ltd., modified dimethylolpropane tri(meth)acrylate, ethylene oxide: SARTOMER SR-454, propylene oxide Trimethylolpropane tri(meth)acrylate; made by Nippon Chemical TPA-310, epichlorohydrin-modified trimethylolpropane tri(meth)acrylate: trimethylolpropane type (meth) acrylate such as DA(M)-321, and pentaerythritol tris(methyl) Acrylate, pentaerythritol tetra(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate: East Asian synthesis ARONIXM-233, dipentaerythritol hexa(meth) acrylate, dipentaerythritol monohydroxy five (a) Acrylate, alkyl modified dipentaerythritol poly(meth) acrylate: KAYARAD D-310, 320, 330, etc., manufactured by Nippon Kasei Co., Ltd., caprolactone modified dipentaerythritol poly(meth) acrylate: Japanese chemical medicine KAYARAD DPCA-20, 30, 60, 120, etc. pentaerythritol type (meth) acrylate, glycerol di(meth) acrylate, epichlorohydrin modified glycerol tri(meth) acrylate: Changchun industry Denacol DA (M)-314, glycerol (meth) acrylate such as triglycerin di(meth) acrylate, dicyclopentenyl di(meth) acrylate, tricyclopentenyl di(methyl) Acrylate, cyclohexyl di(meth)acrylate, methoxycyclohexyl di(meth)acrylate: Shanyang Guoce PLUP CAM-200 and other fats Formula (meth) acrylate, ginseng (propylene oxyethyl) trimeric isocyanate: East Asian synthesis of ARONIX M-315, ginseng (methacryloxyethyl) trimeric isocyanate, caprolactone modified ginseng ( A trimeric isocyanate type (meth) acrylate such as propylene methoxyethyl) trimeric isocyanate or caprolactone modified ginseng (methacryloxyethyl) isocyanurate.

In the compound having an ethylenically unsaturated group, an aromatic compound is exemplified. For example, hydroquinone, resorcin, catechol, gallic phenol, bisphenol A di(meth) acrylate, ethylene oxide (propylene oxide) modified bisphenol A di(methyl) Acrylate [the so-called "ethylene oxide (propylene oxide)" means "Ethylene oxide" or "propylene oxide", the same as the following], bisphenol F di(meth)acrylate, ethylene oxide (propylene oxide) modified bisphenol F di(meth)acrylate, Bisphenol S di(meth)acrylate, ethylene oxide (propylene oxide) modified bisphenol S di(meth)acrylate, epichlorohydrin modified di(meth)acrylate, etc. Aromatic (meth) acrylate compound; tetrachlorobisphenol S ethylene oxide (propylene oxide) modified di(meth) acrylate, tetrabromobisphenol S ethylene oxide (propylene oxide) A styrene-based or (meth) acrylate compound having an aromatic group substituted with a halogen atom having an atomic weight of a chlorine atom or more, such as a modified di(meth)acrylate.

Further, from the viewpoint of coating film strength and scratch resistance, polyfunctional groups such as ethyl urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate can be used ( A methyl acrylate is suitably used as the compound (C). The epoxy group (meth) acrylate is esterified with (meth)acrylic acid to epoxylate the epoxy group of the epoxy resin, and the functional group is (meth)acrylated, and the bisphenol A type epoxy resin is used. (Meth)acrylic acid adduct, (meth)acrylic acid adduct for novolac type epoxy resin, and the like. The ethyl urethane (meth) acrylate is, for example, obtained by reacting a diisocyanate with a (meth) acrylate having a hydroxyl group; and reacting the polyol with the polyisocyanate under an excess of an isocyanate group, and then The obtained isocyanate group-containing ethyl urethane prepolymer is obtained by reacting a (meth) acrylate having a hydroxyl group. Or, the polyol can be reacted with the polyisocyanate under the condition of excess hydroxyl group, and the formed hydroxyl group-containing ethyl carbamate prepolymer and the (meth) acrylate having an isocyanate group can be formed. The winner of the class reaction.

As a commercial item, the following can be illustrated.

Made in East Asia Synthetic Co., Ltd.: ARONIX M-400, ARONIX M-402, ARONIX M-310, ARONIX M-408, ARONIX M-450, ARONIX M-7100, ARONIX M-8030, ARONIX M-8060; Osaka Organic Chemistry Industrial Co., Ltd.: VISCOAT #400; Chemical SARTOMER Co., Ltd.: SR-295; DAICEL UCB Co., Ltd.: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602; Xinzhongcun Chemical Industry Co., Ltd.: NK Ester A-TMMT, NK Oligo A-1020, NK Oligo EMA-1020, NK Oligo EA-6310, NK Oligo EA-6320, NK Oligo EA-6340, NK Oligo MA-6, NK Oligo U -4HA, NK Oligo U-6HA, NK Oligo U-324A; manufactured by BASF: Laromer EA81; manufactured by Sannopco Co., Ltd.: photomer 3016; manufactured by Arakawa Chemical Industries Co., Ltd.: BEAMSET 371, BEAMSET 575, BEAMSET 577, BEAMSET 700 BEAMSET 710; manufactured by Gensei Industrial Co., Ltd.: Artregin UN-3320HA, Artregin UN-3320HB, Artregin UN-3320HC, Artregin UN-3320HS, Artregin UN-9000H, Artregin UN-901T, Artregin HDP, Artregin HDP-3, Artregin H6 1; Japan Synthetic Chemical Industry Co., Ltd.: Violet UV-7600B, Violet UV-7610B, Violet UV-7620EA, Violet UV-7630B, Violet UV-1400B, Violet UV-1700B, Violet UV-6300B; manufactured by Kyoeisha Chemical Co., Ltd.: LIGHT-ACRYLATE PE-4A, LIGHT-ACRYLATE DPE-6A, UA-306H, UA-306T, UA-306I; Japan Chemical Pharmaceutical Co., Ltd.: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330, SR-35;

As described above, the compound (C) containing a photosensitive ethylenically unsaturated group is usually blended in a photosensitive solder resist ink or the like. For example, it is known that a carboxyl group-containing compound can improve the developability or thermosetting property of the composition, and the hydroxyl group is contained. The compound can increase the adhesion or developability of the composition to the substrate. Therefore, the same is true in the present invention, in the case of improving the developability or thermosetting property of the composition, the use of a carboxyl group-containing compound [only, without the above-mentioned carboxyl group-containing urethane resin (A)" Further, the compound (C) containing a photosensitive ethylenically unsaturated group is preferred, and when the adhesion or developability of the composition to the substrate is improved, it is preferred to use a hydroxyl group-containing compound. Moreover, it is preferable that two or more polyfunctional compounds having an ethylenically unsaturated group can be used to improve the photosensitivity or resolution of the composition, and the aromatic unsaturated compound is used for heat resistance of the coating film. Lift or refractive index control. For the purpose of improving the film strength or the scratch resistance, it is preferred to further use an oligomer type (meth)acrylic acid such as ethyl urethane (meth) acrylate or epoxy (meth) acrylate. ester.

Further, the molecule contains an ethylene oxide addition structure or a glycerin-modified (meth) acrylate (for example, ARONIX M-310 manufactured by Toagosei Co., Ltd., SR-355 manufactured by Nippon Kayaku Co., Ltd., etc.) Due to hydrophilicity In the present invention, it is possible to obtain a photosensitive resin composition which is excellent in developability and resolution, and is particularly preferable in the present invention.

The photosensitive ethylenically unsaturated group-containing compound (C) is preferably used in an amount of 0.1 to 300 parts by weight, preferably 0.5 to 100 parts by weight based on 100 parts by weight of the carboxyl group-containing photosensitive urethane resin (A). 200 parts by weight, more preferably 5 to 100 parts by weight. The compound (C) containing a photosensitive ethylenically unsaturated group is used for the purpose of adjusting the photosensitivity and resolution of the photosensitive resin composition. When it is less than 0.1 part by weight, the photosensitive resin composition may have insufficient photosensitivity, and when it exceeds 300 parts by weight, there is a problem in that the flexibility is problematic.

The photosensitive resin composition of the present invention is furthermore than the carboxyl group-containing photosensitive urethane resin (A), the photopolymerization initiator (B), and the photosensitive ethylenically unsaturated compound (C). The thermosetting compound (D) is preferably contained, and the thermosetting compound (D) and the thermosetting assistant (E) are more preferably contained.

The thermosetting compound (D) will be described. The thermosetting compound (D) is not particularly limited as long as it has two or more functional groups reactive with the functional group contained in the carboxyl group-containing photosensitive urethane resin (A). In the present invention, the functional group reactive with the thermosetting compound (D) is preferably a hydroxyl group or a carboxyl group in the carboxyl group-containing photosensitive urethane resin (A).

Examples of the thermosetting compound (D) having at least two functional groups reactive with a hydroxyl group include a polyisocyanate compound and an amine-based tree. Lipid, phenolic resin, polyfunctional polycarboxylic anhydride.

The polyisocyanate compound is not particularly limited as long as it has a compound having an isocyanate group in the molecule. Examples of the polyisocyanate compound include methylphenyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, benzodimethyl diisocyanate, hydrogenated dimethyl diisocyanate, and diphenyl. a polyisocyanate compound such as methane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl dimethyl diisocyanate, stilbene diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and the like, and Addition of such a polyisocyanate compound to a polyol compound such as trimethylolpropane, a dropper or isomeric cyanate of the polyisocyanate compound, or even such a polyisocyanate compound An adduct of an ether polyol or a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprenediol polyol, or the like.

Examples of the amine-based resin and the phenol resin include urea, melamine, and benzopyrene. (benzoguanamine), an addition compound of a compound such as phenol, cresol or bisphenol with formaldehyde or a partial condensate thereof.

The polyfunctional polycarboxylic acid anhydride is not particularly limited as long as it has two or more carboxylic anhydride groups, and examples thereof include tetracarboxylic dianhydride, hexacarboxylic acid trihydride, hexacarboxylic dianhydride, and maleic anhydride. A polycarboxylic acid anhydride such as a polymer resin. Further, a polycarboxylic acid, a polycarboxylate or a polycarboxylic acid half ester which forms an anhydride by a dehydration reaction in the reaction, and a "compound having two or more carboxylic anhydride groups" in the present invention are also included.

More specifically exemplified, the tetracarboxylic dianhydride may be exemplified by pyranic anhydride, diphenyl ketone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, or oxydiphenyl phthalate. Acid dianhydride, diphenyl sulfonic acid tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, new Japanese physicochemical "RIKACID TMTA-C", "RIKACID MTA-10", "RIKACID MTA-15", "RIKACID TMEG Series", "RIKACID TDA", etc.

Examples of the maleic anhydride copolymerized resin include a styrene-maleic anhydride copolymer resin such as SMA resin series manufactured by SARTOMER Co., Ltd., and a GSM series manufactured by Kyori SHELLAC Co., Ltd., and p-phenylbenzene. Ethylene-maleic anhydride copolymerized resin, α-olefin-maleic anhydride copolymerized resin such as polyethylene-maleic anhydride, "VEMA" manufactured by DAICEL Chemical Industry Co., Ltd. (methyl vinyl ether and A copolymer of maleic anhydride), a maleic anhydride acrylic modified polyolefin ("AUROREN series" manufactured by Nippon Paper Chemical Co., Ltd.), a maleic anhydride copolymerized acrylic resin, or the like.

Examples of the thermosetting component (D) having at least two functional groups reactive with a carboxyl group include a compound (k) having two or more epoxy groups or oxocyclobutane groups, and a polyfunctional vinyl ether. Compounds, high molecular weight polycarbodiimides, aziridine compounds, and the like. Among them, the compound (k) having two or more epoxy groups or oxocyclobutane groups is very suitable from the viewpoint of the curing rate and the durability of the cured product.

The compound (k) having two or more epoxy groups or oxocyclobutane groups is not particularly limited as long as it has two or more epoxy groups or oxocyclobutane groups in the molecule. The compound (k) is a compound having an epoxy group, and specific examples thereof include ethylene glycol diglycidyl ether and polyethylene glycol. Diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A‧ epichlorohydrin type epoxy resin, bisphenol F‧ epichlorohydrin type epoxy resin, biphenyl ‧ epichlorohydrin type Epoxy resin, glycerol, polyglycidyl ether of epichlorohydrin adduct, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and second ring disclosed in Japanese Patent Laid-Open Publication No. 2001-240654 Pentadiene type epoxy resin, naphthalene type epoxy resin, polyglycidyl ether of ethylene glycol/epichlorohydrin adduct, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, polybutylene Diene diglycidyl ether, hydroquinone diglycidyl ether, dibromo neopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, six Diglycidyl ether hydride, hydrogenated bisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether, N, N, N', N'-tetraglycidyl metaxylene diamine, 1, 3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N-diglycidylaniline, N,N-diglycidyltoluidine An epoxy compound excellent in flexibility disclosed in Japanese Laid-Open Patent Publication No. 2004-156777, JP-A-2004-315777, or JP-A-2004-323777, or the following formulas (1) to (3) Constructed epoxy compounds, etc.

[Chemical 2]

Further, the compound (k) is a compound having an oxocyclobutane group, and specifically, 4,4'-bis[(3-ethyl-3-oxocyclobutane)methoxymethyl group can be exemplified. Biphenyl, (2-ethyl-2-oxocyclobutane) ethanol and terephthalic acid ester, (2-ethyl-2-oxocyclobutane) ethanol and novolak resin An etherified product, an esterified product of (2-ethyl-2-oxocyclobutane)ethanol and a polyvalent carboxylic acid compound, or the like.

The compound (k), an aliphatic epoxy compound, or an epoxy compound of JP-A-2004-156024, JP-A-2004-315595, and JP-A-2004-323777 are softened by a cured coating film. Excellent, so it is especially good. Further, a dicyclopentadiene type epoxy compound or a phenol-novolac type epoxy resin, a cresol novolak type epoxy resin, a biphenyl type and an epichlorohydrin type ring are disclosed in Japanese Laid-Open Patent Publication No. 2001-240654. Oxygen resin, 4,4'-bis[(3-ethyl-3-oxocyclobutane)methoxymethyl]biphenyl, (2-ethyl-2-oxocyclobutane)ethanol In the present invention, esterified with terephthalic acid or the like is preferable in terms of durability of the cured coating film such as thermosetting property, moisture absorption property, and heat resistance.

Specific examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and tetraethylene glycol divinyl ether. , pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1, 6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane Alkenyl divinyl ether, hydroquinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcinol divinyl ether, ethylene oxide modified bisphenol A Divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerol trivinyl ether, Pearitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, di-trimethylol Propane tetravinyl ether, di-trimethylolpropane polyvinyl ether, and the like.

The high molecular weight polycarbodiimide is the Carbodilite series of Nisshin Textile Co., Ltd. Among them, Carbodilite V-01, 03, 05, 07, 09 is excellent in compatibility with an organic solvent.

Examples of the indole cyclopropane compound include 2,2'-bishydroxymethylbutanol gin [3-(1-indolyl)propionate], and 4,4'-bis (extended ethyl group). Aminocarbonylamino)diphenylmethane or the like.

As the other thermosetting compound (D), benzo is added as long as it is permeated by heating. (benzoxazine) compound, benzocyclobutene compound, maleimide compound, nadimide compound, allyl nadic ylide compound, melamine compound, hydrazine A compound which is hardened by a compound such as a guanamine compound or a blocked isocyanate compound can be effectively used. These compounds having a photopolymerizable group or a functional group reactive with a carboxyl group and a functional group reactive with a hydroxyl group can be used particularly effectively because the heat resistance of the coating film after curing can be improved.

These thermosetting compounds (D) may be used alone or in combination of two or more. The amount of the thermosetting compound (D) to be used is determined in consideration of the use of the photosensitive resin composition, etc., and is not particularly limited, and is 100 parts by weight based on 100 parts by weight of the carboxyl group-containing photosensitive urethane resin (A). It is preferably in the range of 0.1 part by weight to 100 parts by weight, more preferably in the range of 0.5 part by weight to 80 parts by weight. Thereby, since the crosslinking density of the photosensitive resin composition can be adjusted to an appropriate value, various physical properties of the photosensitive resin composition can be further improved. When the amount of the thermosetting compound (D) used is less than 0.1 part by weight, the crosslinking density of the coating film after heat curing is too low, and cohesive force or durability is insufficient. In addition, when the amount used exceeds 100 parts by weight, the crosslinking density after heat curing is too high, and as a result, the coating film bendability and flexibility are lowered, and even the back warpage of the substrate is remarkably deteriorated.

Next, the heat hardening aid (E) will be described. In the present invention, the thermosetting assistant means a compound which directly or catalytically contributes to a hardening reaction at the time of thermosetting.

The thermosetting assistant (E) can be appropriately selected depending on the thermosetting compound (D) to be used. Further, the curing conditions of the carboxyl group-containing photosensitive urethane resin (A) and the thermosetting compound (D) can be appropriately selected depending on the thermosetting compound (D) or the thermosetting auxiliary (E) to be used. select.

Examples of the thermosetting assistant (E) include triethylamine, tributylamine, benzyldimethylamine, and 2,4,6-cis (dimethylaminomethyl)phenol. N-methylper Grade 3 amines and their salts; 2-methylimidazole, 2-phenylimidazole, 2-lauryl imidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methyl Imidazole, 2,4-dicyano-6-[2-methylimidazolinyl-1]-ethyl-S-three Imidazoles and their salts; 1,5-diazabicyclo[5,4,0]-7-octadecane, 1,5-diazabicyclo[4,3,0]-5-oxime a diazabicyclic compound such as an alkene or a 1,4-diazabicyclo[2,2,2]octane; a tributylphosphine, a triphenylphosphine or a bis(dimethoxyphenyl)phosphine; a phosphine such as hydroxypropylphosphine or cyanoethylphosphine; tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylguanidinium An onium salt such as a tetraphenylborate; or a compound which is a catalytic property and which directly contributes to a hardening reaction, may be dicyanodiamine or carboxylic acid hydrazine. Examples of the carboxylic acid lanthanum include cesium succinate and cesium adipate.

In the present invention, in the case where an epoxy compound is used as the curable compound (D), as the thermosetting assistant (E), if dicyanoguanamine, carboxylic acid hydrazine, imidazole or diazide is used, The cyclic compound is preferred because it can perform a thermosetting reaction more effectively and has excellent coating film resistance.

Further, in the present invention, the thermosetting auxiliary (E) is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the photosensitive urethane resin (A) containing a carboxyl group. It is more preferably in the range of 0.5 to 8 parts by weight. When used in an amount of less than 0.1 parts by weight, it cannot be used as heat The effect of the hardening aid is sufficient, and there is a case where the final film cohesion or durability is insufficient. In addition, when the amount is more than 10 parts by weight, the excess heat curing auxiliary agent remains in the system, and the physical properties of the coating film may deteriorate due to bleeding or deterioration of insulation properties.

The photosensitive resin composition of the present invention may contain a resin other than the above-mentioned carboxyl group-containing photosensitive urethane resin (A) or a photosensitive ethylenically unsaturated group-containing compound (C). Examples of the resin other than the photosensitive urethane resin (A) containing a carboxyl group or the compound (C) containing a photosensitive ethylenically unsaturated group include an acrylic resin, a polyester resin, and a urethane. An ester resin, a urea resin, a urethane urea resin, an epoxy resin, a polyamide resin, a polyimide resin, or the like. These are preferably those containing a carboxyl group from the viewpoint of developability, and further, a photosensitive urethane resin (A) containing a carboxyl group or a compound (C) containing a photosensitive ethylenically unsaturated group. The compatibility is superior. In the present invention, in the case of a resin other than the photosensitive urethane resin (A) containing a carboxyl group or the compound (C) containing a photosensitive ethylenically unsaturated group, they may be used singly or in combination.

Further, a solvent, a dye, a pigment, a flame retardant, an antioxidant, a polymerization inhibiting agent, a smoothing agent, a moisturizing agent which is an optional component may be further added to the photosensitive resin composition of the present invention in a range which does not impair the purpose. , viscosity modifier, preservative, antibacterial agent, antistatic agent, anti-blocking agent, ultraviolet absorber, infrared absorber, electromagnetic wave shielding agent, filler, etc. In particular, the use of insulating members (such as circuit protection films, covering layers, interlayer insulating materials, etc.) or circuit circuits that are in direct contact with the circuit in the use of electronic materials When a member having high heat (a printed wiring board adhesive, a supporting substrate, or the like) is used, it is preferable to use a flame retardant in combination.

Examples of the flame retardant include melamine phosphate, melamine polyphosphate, strontium phosphate, strontium polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amide ammonium phosphate, ammonium polyphosphate ammonium phosphate, urethane phosphate, and polyphosphoric acid amine. a phosphate compound or a polyphosphate compound such as a formate; red phosphorus, an organic phosphate compound, a phosphazene compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound Phosphorus-based flame retardants such as phosphorane compounds, phosphor phthalamide compounds; melamine, melam, melem, melon, melamine cyanuric acid Ester, etc. a compound; a cyanuric compound, a cyanuric acid compound, a triazole compound, a tetrazole compound, a diazo compound, a nitrogen-based flame retardant such as urea; a fluorene-based flame retardant such as an anthrone compound or a decane compound; Halogenated halogen-containing compounds such as halogenated bisphenol A, halogenated epoxy compounds, halogenated phenoxy compounds, halogen-based flame retardants such as halogenated oligomers or polymers; aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, Metal hydroxide such as barium hydroxide or calcium hydroxide; tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, cerium oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, boric acid An inorganic flame retardant such as zinc or hydrated glass. In the present invention, in consideration of the influence on the environment in recent years, it is preferable to use a non-halogen flame retardant such as a phosphorus-based flame retardant or a nitrogen-based flame retardant, and in combination, the photosensitive agent of the present invention is used in combination. As the resin composition, a phosphorus-nitrogen compound, a phosphonic acid compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate or the like which is effective due to flame retardancy is preferably used. In the present invention, the flame retardants may be used singly or in combination.

Since the photosensitive resin composition of the present invention and the cured product thereof are excellent in alkali developability, they can be suitably used in applications including a coating film forming process including photocuring, alkali developing, and post-cooking. In addition, since it is excellent in solder heat resistance and coating film resistance, and is excellent in flexibility and flexibility, it can be suitably used for a solder resist ink or a photosensitive cover film for a flexible printed wiring board.

The photosensitive resin composition of the present invention can be applied to a metal, ceramic, glass, plastic, wood, slate or the like as a substrate, and is not particularly limited. Examples of the specific plastics include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triethyl fluorenyl cellulose resin, ABS resin, AS resin, polyamine, and ring. Oxygen resin, melamine resin, etc. Moreover, the shape of the substrate is not limited to a film sheet, a plate-shaped panel, a lens shape, a dish shape, or a fiber shape.

The photosensitive resin composition of the present invention can be cured by a known radiation curing method to obtain a cured product, and an electron beam, an ultraviolet ray, and visible light of 400 to 500 nm can be used as an active energy ray. As the source of the electron beam to be irradiated, a thermal electron ray gun, an electric field radiant gun, or the like can be used. Further, as the ultraviolet light and the visible light source (light source) of 400 to 500 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp or the like can be used. Specifically, in terms of point light sources and brightness stability, ultrahigh pressure mercury lamps, mercury lamps, and metal halide lamps are often used. The amount of the active energy ray to be irradiated can be appropriately set in the range of 5 to 2000 mJ/cm ² , and is easy to manage in engineering, and is preferably in the range of 50 to 1000 mJ/cm ² . Further, the active energy rays can be used together with heat caused by infrared rays, far infrared rays, hot air, high frequency heating, or the like.

When the photosensitive resin composition of the present invention is used as an optical solder resist, it can be used as a liquid solder resist ink dissolved in a solvent or a dry film type solder resist which is dried in advance.

When it is used as a liquid solder resist ink, the photosensitive resin composition of the present invention is applied to a substrate, and after being volatilized by natural or forced drying, the solvent may be cured by radiation or after coating. After radiation hardening, natural or forced drying may also be carried out, preferably after natural or forced drying. Further, in the case of the liquid solder resist ink, it is preferable that the storage step, the coating step, and the like are completed until the application of the substrate is completed, since the solvent is not volatilized during the treatment, and therefore, as the resin is synthesized, The solvent used in the preparation of the solvent or ink is preferably a high boiling point. For example, it is particularly preferable to use carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone or the like. Further, in the case of the liquid solder resist ink, in consideration of storage stability or handleability, a two-liquid type in which a curing agent is additionally stored in advance and a curing agent is mixed as needed before coating is considered. In the case of the present invention, the photopolymerization initiator (B), the thermosetting compound (D), the thermosetting assistant (E), and the rest of the materials may be stored separately as a two-component type.

On the other hand, in the case of being used as a dry film type solder resist, first, a photosensitive composition dissolved in a solvent is applied onto a film substrate having a good release property such as a separation film, and then the solvent is dried. And making dry film type solderproof Agent. In this case, the solvent to be used is different from the above liquid solder resist ink, and since it is necessary to completely dry the solvent in a short time, it is preferred to use a solvent having a low boiling point. For example, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isobutanol or the like can be preferably used. The dry film formed on the separation film is bonded to a copper circuit or the like formed on the polyimide, and then removed by lamination or vacuum lamination to adhere the cells and the like. After the bonding step, there is a case where the radiation is hardened by the separation film, or the separation film is peeled off, and the development pattern is contacted to perform radiation hardening. When the developing pattern is brought into contact and radiation hardened, since there is a tack on the dry film and the developed pattern is contaminated, the dry film type solder resist is required to have less stickiness. Since the photosensitive resin composition of the present invention can reduce the viscosity as needed, it can be effectively used as a dry film solder resist.

Further, after the radiation-curing composition of the present invention is further subjected to radiation curing, a pattern is formed by development, and thermal curing is performed as a post-ripening step to form a film having excellent resistance. The post-cooking treatment is preferably carried out at 100 ° C to 200 ° C for 30 minutes to 2 hours. Further, in order to further improve the coating film resistance, after the post-cooking, the active energy ray may be irradiated as needed. Solder heat resistance and the like can be further improved by irradiating the active energy ray after the post-cooking.

[Examples]

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. In addition, the "parts" of the examples mean "parts by weight".

In addition, the measurement conditions of GPC are as follows.

<Measurement of Weight Average Molecular Weight (Mw)> The measurement of Mw was carried out by GPC (gel permeation chromatography) "HPC-8020" manufactured by Tosoh Corporation. GPC is a liquid chromatography method in which a substance dissolved in a solvent (THF: tetrahydrofuran) is separated and quantified by a difference in molecular size thereof. In the measurement system of the present invention, "LF-604" (made by Zhaohe Electric Co., Ltd.: GPC column for rapid analysis: 6 mm ID × 150 mm size) is continuously used in series in two columns at a flow rate of 0.6 ml/min, and the tube is used. The column temperature was 40 ° C, and the weight average molecular weight (Mw) was determined in terms of polystyrene.

[Manufacturing Example 1]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 156 parts, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 13,000 in terms of polystyrene and an actually measured resin solid value of 98 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization prohibition. The hydroquinone of the stopper was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 14800 in terms of polystyrene and an actual measured acid value of 8 mgKOH/g of the resin.

Next, 63 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin prepared by the present production method is 863 g/eq, and the weight average molecular weight in terms of polystyrene is 15,400, and the actually measured resin is solid. The acid value was 73 mgKOH/g.

[Manufacturing Example 2]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 4 parts, 201 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 296 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of urethane. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing urethane prepolymer having a weight average molecular weight of 8900 in terms of polystyrene and an actual measured acid value of 152 mgKOH/g of the resin.

Next, stop the nitrogen from the nitrogen introduction tube of the flask and switch to Into the introduction of dry air, 193 parts of glycidyl methacrylate and 7 parts of dimethylbenzylamine were added while stirring, and 0.4 parts of hydroquinone as a polymerization inhibiting agent was further added, and the reaction was carried out at 90 ° C for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 9,600 in terms of polystyrene and an actually measured resin solid content of 1 mgKOH/g.

Next, 136 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin component of the carboxyl group-containing photosensitive urethane resin prepared by the present production example is 611 g/eq, and the weight average molecular weight in terms of polystyrene is 1,020, and the actually measured resin is solid. The acid value was 92 mgKOH/g.

[Manufacturing Example 3]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 318 parts, 46 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 136 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of urethane. After the completion of the reaction, a small amount of sampling was carried out to obtain a polystyrene-converted weight average molecular weight of 19,800, and the actually measured resin solid content of the acid value of 35 mgKOH/g of the carboxyl group Base urethane prepolymer.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 44 parts of glycidyl methacrylate and 5 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 22,000 in terms of polystyrene and an actual measured resin having an acid value of 3 mgKOH/g.

Next, 31 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by the present production example was 1846 g/eq, and the weight average molecular weight in terms of polystyrene was 23,100, and the actually measured resin solid content was determined. The acid value was 30 mgKOH/g.

[Manufacturing Example 4]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) In an amount of 115 parts, 115 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 244 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the reaction is over, proceed A small amount of sample was obtained, and a polystyrene-converted weight average molecular weight of 48,900 was obtained, and the actually measured resin solid content was 87 mgKOH/g of a carboxyl group-containing urethane prepolymer.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 52,200 in terms of polystyrene and an actual measured acid value of 5 mg KOH/g of the resin.

Next, 78 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by the present production example is 884 g/eq, and the weight average molecular weight in terms of polystyrene is 54,000, and the actually measured resin solid content The acid value was 68 mgKOH/g.

[Manufacturing Example 5]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 164 parts, 135 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, in the flask 202 parts of isophorone diisocyanate was added thereto, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing urethane prepolymer having a weight average molecular weight of 3,900 in terms of polystyrene and an actual measured resin having an acid value of 102 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 103 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 4,600 in terms of polystyrene and an actual measured resin having an acid value of 17 mgKOH/g.

Next, 65 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin prepared by the present invention is 920 g/eq, and the weight average molecular weight in terms of polystyrene is 5,100, and the actually measured resin is solid. The acid value was 71 mgKOH/g.

[Manufacturing Example 6]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) ) 156 parts, dimethylolbutanoic acid (Japan Chemical Industry Co., Ltd.) 129 parts of 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 13,000 in terms of polystyrene and an actually measured resin solid value of 98 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and hydroxypropyl 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.: 4-HBAGE) was added while stirring. Further, 7 parts of dimethylbenzylamine was further added to 0.3 parts of hydroquinone as a polymerization inhibiting agent, and the reaction was carried out at 90 ° C for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 16,500 in terms of polystyrene and an actual measured resin having an acid value of 9 mgKOH/g.

Next, 70 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by the present production example is 931 g/eq, and the weight average molecular weight in terms of polystyrene is 18,800, and the actually measured resin solid content The acid value was 65 mgKOH/g.

[Manufacturing Example 7]

With a mixer, reflux cooling tube, nitrogen inlet tube, inlet tube, temperature In a four-necked flask, 146 parts of polytetramethylene glycerol (PTG1000sn: hydroxy valence = 1010 KOH/g) and dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) were added. 129 parts of 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 13,000 in terms of polystyrene and an actually measured resin solid value of 98 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 14800 in terms of polystyrene and an actual measured acid value of 8 mgKOH/g of the resin.

Next, 107 parts of tetrahydrophthalic anhydride (manufactured by Nippon Chemical Co., Ltd.: RIKACID TH) was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by the production example is 920 g/eq, and the weight average molecular weight in terms of polystyrene is 16500, and the actual measured acid value of the resin was 62 mgKOH/g.

[Manufacturing Example 8]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 156 parts, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 13,000 in terms of polystyrene and an actually measured resin solid value of 98 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 55 parts of glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether were added while stirring (Japan Chemicals Co., Ltd.) The company made: 78 parts of 4-HBAGE, 7 parts of dimethylbenzylamine, and further added 0.3 parts of hydroquinone as a polymerization inhibitor, and carried out a reaction at 90 ° C for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 16,900 in terms of polystyrene and an actual measured resin solid content of 7 mgKOH/g.

Next, 72 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In FT-IR measurement, indeed After the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin prepared by the present production method is 885 g/eq, and the weight average molecular weight in terms of polystyrene is 17,300, and the actually measured resin is solid. The acid value was 68 mgKOH/g.

[Manufacturing Example 9]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 156 parts, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 13,000 in terms of polystyrene and an actually measured resin solid value of 98 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 14800 in terms of polystyrene and an actual measured acid value of 8 mgKOH/g of the resin.

Next, 53 parts of tetrahydrophthalic anhydride (manufactured by Nippon Chemical Co., Ltd.: RIKACID TH) and 35 parts of succinic anhydride were added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin prepared by the present invention is 840 g/eq, and the weight average molecular weight in terms of polystyrene is 17,100, and the actually measured resin is solid. The acid value was 72 mgKOH/g.

[Manufacturing Example 10]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 156 parts, 128 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing urethane prepolymer having a weight average molecular weight of 14100 in terms of polystyrene and an actual measured resin having an acid value of 97 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 133 parts of oxetanyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization prohibition. The hydroquinone of the stopper was 0.3 parts, and the reaction at 95 ° C was carried out for 16 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 15100 in terms of polystyrene and an actually measured resin solid content of 7 mgKOH/g.

Next, 70 parts of succinic anhydride was added to the flask, and the mixture was reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin prepared by the present production method is 901 g/eq, and the weight average molecular weight in terms of polystyrene is 16,300, and the actually measured resin is solid. The acid value was 69 mgKOH/g.

[Manufacturing Example 11]

A polycarbonate diol (Kuraray Polyol C-1090: manufactured by Kuraray Co., Ltd.: hydroxyvalence = 1212 mgKOH/g, Mw) was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer. =1002) 156 parts, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), 375 parts of cyclohexanone as a solvent, and the mixture was heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing urethane prepolymer having a weight average molecular weight of 23,100 in terms of polystyrene and an actual measured resin having an acid value of 100 mgKOH/g.

Next, stop the nitrogen from the nitrogen introduction tube of the flask and switch to Into the introduction of dry air, 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and 0.3 parts of hydroquinone as a polymerization inhibiting agent was further added, and the reaction was carried out at 90 ° C for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 24,600 in terms of polystyrene and an actual measured resin having an acid value of 7 mgKOH/g.

Next, 63 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive urethane resin prepared by the present invention is 870 g/eq, and the weight average molecular weight in terms of polystyrene is 25,500, and the actually measured resin solid content The acid value was 70 mgKOH/g.

[Manufacturing Example 12]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 156 parts, 129 parts of dimethylolpropionic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Next, 215 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours to carry out a reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a polystyrene-converted weight average molecular weight of 18,700, and the actually measured resin solid content of the acid value of 102 mgKOH/g of the carboxyl group was contained. Base urethane prepolymer.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing urethane prepolymer having a weight average molecular weight of 20,200 in terms of polystyrene and an actual measured resin having an acid value of 6 mgKOH/g.

Next, 63 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by the present production example is 851 g/eq, and the weight average molecular weight in terms of polystyrene is 22,600, and the actually measured resin solid content The acid value was 74 mgKOH/g.

[Manufacturing Example 13]

Polytetramethylene glycerol was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyl value = 110 mgKOH/g, Mw = 1020) 156 parts, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.), and 375 parts of cyclohexanone as a solvent were heated to 60 ° C while stirring under a nitrogen stream, and uniformly dissolved. Then, 215 parts of methyl benzene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) was added to the flask, and the mixture was stirred at 90 ° C for 8 hours. The reaction of urethane is carried out. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 24,500 in terms of polystyrene and an actually measured resin having an acid value of 99 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing urethane prepolymer having a weight average molecular weight of 26,300 in terms of polystyrene and an actually measured resin solid content of 11 mgKOH/g.

Next, 63 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, it was cooled to room temperature. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin component of the carboxyl group-containing photosensitive urethane resin prepared by the present production example is 858 g/eq, and the weight average molecular weight in terms of polystyrene is 27,400, and the actually measured resin solid content The acid value was 67 mgKOH/g.

The physical properties of the carboxyl group-containing urethane resin obtained in Production Examples 1 to 13 are shown in Table 1.

1) PTG1000sn... (made by Baotu Valley Chemical Co., Ltd.: polytetramethylene glycerol) 2) DMBA... (made by Nippon Kasei Co., Ltd.: dimethylolbutanoic acid) 3) IDPI... (isophorone diisocyanate) 4) GMA...(glycidyl methacrylate) 5)SA...(succinic anhydride) 6)4HBAGE...(4-hydroxybutyl acrylate glycidyl ether) 7)TH...(tetrahydrophthalic anhydride) 8) OXMA... (oxocyclobutane methacrylate) 9) C-1090... (manufactured by Kuraray Co., Ltd.: polycarbonate diol) 10) DMPA... (manufactured by Nippon Kasei Co., Ltd.: dihydroxy Methyl propionic acid) 11) XDI... (Mitsui Chemical Polyurethane Co., Ltd.: methyl phthalate diisocyanate)

[Manufacturing Example 14]

A bisphenol A ring having an epoxy equivalent of 650, a softening point of 81.1 ° C, and a melt viscosity (150 ° C) of 12.5 poise was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer. 371 parts of an oxyresin, 925 parts of epichlorohydrin, and 463 parts of dimethyl hydrazine were uniformly dissolved, and then 52.8 parts of a 98.5% sodium hydroxide aqueous solution was added at 70 ° C for 100 minutes while stirring. After the addition, the reaction was further carried out at 70 ° C for 3 hours. Next, the excess unreacted epichlorohydrin and most of the dimethyl hydrazine are distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl hydrazine is dissolved in methyl isobutyl ketone. After 750 parts, 10 parts of a 30% aqueous sodium hydroxide solution was further added, and the reaction was carried out at 70 ° C for 1 hour. After the reaction is over, The water was washed twice with 200 parts of water. After the oil-water separation, methyl isobutyl ketone was distilled from the oil layer to obtain 340 parts of an epoxy resin having an epoxy equivalent of 287, a hydrolyzable chlorine content of 0.07%, a softening point of 64.2 ° C, and a melt viscosity (150 ° C) of 7.1 poise.

287 parts of the epoxy resin was added to a four-necked flask of another stirrer, a reflux cooling tube, a nitrogen introduction tube, an introduction tube, and a thermometer, and further added 72 parts of acrylic acid, 0.3 parts of methylhydroquinone, and 194 parts of cyclohexanone. The reaction mixture was dissolved by heating and stirring at 90 °C. Next, the reaction liquid was cooled to 60 ° C, and 1.7 parts of triphenylphosphine was added, and the reaction was carried out at 100 ° C for about 32 hours in the presence of oxygen to obtain a reactant which actually measured an acid value of 1 mgKOH/g. Next, 78 parts of succinic anhydride and 42 parts of cyclohexanone were added thereto, and the reaction was carried out at 95 ° C for about 6 hours to obtain a carboxyl group-containing photosensitive resin whose main skeleton was a bisphenol A type epoxy resin. Further, cyclohexanone was added to the solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin of the bisphenol A type epoxy resin prepared by the present production method is 450 g/eq, and the weight average molecular weight in terms of polystyrene is 7400, and the actually measured acid value of the resin is determined. It is 100 mgKOH/g.

[Manufacturing Example 15]

A cresol novolac type epoxy resin (manufactured by Tohto Kasei Co., Ltd.: YDCN-702) having an epoxy equivalent of 218 g/eq was placed in a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube, an introduction tube, and a thermometer. 330 parts were heated and melted at 90 to 100 ° C and stirred. Next, 120 parts of acrylic acid, 0.6 parts of hydroquinone, and 5 parts of dimethylbenzylamine were added, and the temperature was raised to 115 ° C while stirring in the presence of oxygen, and the reaction was carried out 12 hour. Next, 400 parts of cyclohexanone was added to the flask, and the mixture was heated to 70 ° C and dissolved. Further, 81 parts of succinic anhydride was added, and the temperature was raised to 95 ° C, and the mixture was stirred and reacted for 8 hours. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was a cresol novolak skeleton. The addition of cyclohexanone to the solution was continued to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the anhydride modified cresol novolak resin prepared by the present production example is 319 g/eq, and the weight average molecular weight in terms of polystyrene is 11,000, and the actually measured resin solid acid is acid. The price is 85 mgKOH/g.

[Manufacturing Example 16]

In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube, an introduction tube, and a thermometer, a dropping funnel was placed, and 400 parts of cyclohexanone was added to the flask, and the mixture was heated to 90 ° C while stirring under a nitrogen atmosphere, and added thereto. 15 parts of methacrylic acid, 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, 25 parts of benzyl methacrylate, 20 parts of azobisisobutyronitrile as a polymerization initiator, and 100 parts of cyclohexanone , stir and dissolve evenly. The monomer solution was placed in a dropping funnel placed in a flask, and the flask was stirred at 90 ° C under a nitrogen atmosphere, and the monomer solution of the dropping funnel was dropped to the flask over 2 hours. After the completion of the dropwise addition, stirring was continued at 90 ° C. After the completion of the dropwise addition for 2 hours, 0.5 part of azobisisobutyronitrile was added to the flask. After 1 hour, 0.5 part of azobisisobutyronitrile was added to the flask, and stirring was further continued for 2 hours. Thereafter, the flask was cooled and the reaction was stopped. A small amount of sampling was carried out to obtain a carboxyl group-containing acrylic prepolymer having a weight average molecular weight of 18,700 in terms of polystyrene and a resin solid value of 98 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 111 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing acrylic acid prepolymer having a weight average molecular weight of 19,900 in terms of polystyrene and an actual measured resin having an acid value of 5 mgKOH/g.

Next, 63 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, it was confirmed that the absorption of the acid anhydride group disappeared, and then the temperature was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was an acrylic resin. The addition of cyclohexanone to the solution was continued to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the acrylic resin prepared by the present production example was 863 g/eq, the weight average molecular weight in terms of polystyrene was 22,000, and the actually measured acid value of the resin was 70 mgKOH/g.

[Manufacturing Example 17]

In a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, an introduction tube, and a thermometer, 212 parts of polytetramethylene glycerol (PTG850: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyvalide = 129 mgKOH/g) was added. 75 parts of ethylene glycol, 159 parts of pyrogallic anhydride (manufactured by DAICEL Chemical Industry Co., Ltd.), 2 parts of dimethylbenzylamine, and 375 parts of cyclohexanone as a solvent, and stirred at 100 ° C under a nitrogen stream. The mixture was stirred for 10 hours to carry out a half esterification reaction. Next, 54 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours. The reaction of ethyl carbamate. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing urethane prepolymer having a weight average molecular weight of 15200 in terms of polystyrene and an actually measured resin solid value of 170 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 110 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibiting agent. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After cooling, a small amount of sampling was carried out to obtain a carboxyl group-containing photosensitive urethane resin whose main skeleton was an acid anhydride-modified urethane skeleton. Next, cyclohexanone was added to the solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin modified by the acid anhydride modified urethane resin prepared by the present production method is 896 g/eq, and the weight average molecular weight in terms of polystyrene is 18,800, and the actually measured resin solid content is determined. The acid value was 72 mgKOH/g.

[Manufacturing Example 18]

218 parts of polytetramethylene glycerol (PTG850: manufactured by Hodogaya Chemical Co., Ltd.: hydroxyvalence = 129 mgKOH/g) was added to a four-necked flask equipped with a stirrer, a reflux cooling tube, a nitrogen inlet tube, an introduction tube, and a thermometer. 47 parts of ethylene glycol, 125 parts of pyrogallic anhydride (manufactured by DAICEL Chemical Industry Co., Ltd.), 2 parts of dimethylbenzylamine, and 375 parts of cyclohexanone as a solvent, and stirred at 100 ° C under a nitrogen stream. The mixture was stirred for 10 hours to carry out a half esterification reaction. Next, 111 parts of isophorone diisocyanate was added to the flask, and the mixture was stirred at 90 ° C for 8 hours. The reaction of urethane is carried out. After the completion of the reaction, a small amount of sampling was carried out to obtain a carboxyl group-containing urethane prepolymer having a weight average molecular weight of 17,000 in terms of polystyrene and an actually measured resin solid value of 110 mgKOH/g.

Next, the nitrogen gas from the nitrogen introduction tube of the flask was stopped, and the introduction of dry air was switched, and 131 parts of glycidyl methacrylate and 6 parts of dimethylbenzylamine were added while stirring, and further added as a polymerization inhibitor. The hydrogen hydrazine was 0.3 parts, and the reaction at 90 ° C was carried out for 8 hours. After the completion of the reaction, a small amount of sampling was carried out to obtain a hydroxyl group-containing ethyl urethane prepolymer having a weight average molecular weight of 19,200 in terms of polystyrene and an actual measured resin having an acid value of 4 mgKOH/g.

Next, 74 parts of succinic anhydride was added to the flask, and the mixture was further reacted at 90 ° C for 6 hours in a dry air atmosphere. In the FT-IR measurement, after confirming that the absorption of the acid anhydride group disappeared, the mixture was cooled to room temperature to obtain a carboxyl group-containing urethane resin whose main skeleton was an acid anhydride-modified urethane resin. Cyclohexanone was added to the solution to adjust to a solid content of 50.0%. The ethylenically unsaturated group equivalent of the resin solidified by the acid anhydride modified urethane resin prepared by the present production method is 765 g/eq, and the weight average molecular weight in terms of polystyrene is 21,400, and the actually measured resin solid content is determined. The acid value was 67 mgKOH/g.

The physical properties of the resins obtained in Production Examples 14 to 18 are shown in Table 2.

[Example 1]

100.0 parts of a resin varnish (a solution of a carboxyl group-containing urethane prepolymer) obtained in Production Example 1 as an optical polymerization initiator IRGACURE-907 (manufactured by Chiba Special Chemical Co., Ltd.: 2-methyl -1-[4-(methylthio)phenyl]-2- 啉olin-1-propane) 2.5 parts, the same DETX-S (manufactured by Nippon Kayaku Co., Ltd.: 2,4-diethyl 9-oxosulfur 0.25 parts, 22.5 parts of SR-355 (manufactured by Nippon Kayaku Co., Ltd.: di-trimethylolpropane tetraacrylate) as a compound containing a photosensitive ethylenically unsaturated group, uniformly dissolved and mixed, and made a cost invention A photosensitive resin composition.

[Examples 2 to 13]

The resin varnish obtained in Production Examples 2 to 13 was blended in the same ratio as in Example 1 to prepare a photosensitive resin composition containing each resin.

[Comparative Examples 1 to 5]

The resin varnish obtained in Production Examples 14 to 18 was blended in the same ratio as in Example 1 to prepare a photosensitive resin composition containing each resin.

<Evaluation 1> The following evaluation was performed with respect to the photosensitive resin composition obtained.

[Production of Sample A] The obtained photosensitive resin composition was applied to a polyimide film (Kapton 100H: manufactured by Toray Phillips Co., Ltd.: 25 μm thick) so as to have a dry film thickness of 20 μm, and was dried by a hot air dryer at 80 ° C. After drying for 30 minutes, it was cooled to room temperature. Think of this as sample A.

[Production of Sample B] After the sample A was irradiated with ultraviolet light having a cumulative light amount of 300 mJ/cm ² by an ultraviolet exposure apparatus ("UVC-2534/1MNLC3-AA08", one 120 W/cm metal halogen lamp manufactured by Ushio Electric Co., Ltd.), Thermal hardening (post-ripening) was carried out for 1 hour using a hot air dryer at 150 °C. The resulting cured film was cooled to room temperature. Think of this as sample B.

[Production of Sample C] A 21-step (step company) (step by Kodak Co., Ltd.) was placed in close contact with the sample A, and the cumulative amount of light was 150 mJ/illuminated by an ultraviolet exposure apparatus in the same manner as the user who created the sample B. Ultraviolet light of cm ² . Think of this as sample C.

In addition, the ladder type plate refers to a film which is light-shielded by gradually increasing the optical density by 21 segments, is adhered to the test coating film, and is irradiated with light from above the film, and then, when developing, it is tested according to the test. The resolution of the coating film changes the number of peeling sections of the coating film. Therefore, it is used as an indicator for evaluating the analytical properties of the test coating film.

[Evaluation of adhesion] According to JIS K5400, regarding the sample B, the cut pieces were made into a checkerboard shape of 1 mm × 1 mm on the hardened coating film, and the peeling test was performed by Scotch tape (registered trademark). The peeling state of the checkerboard cut pieces was observed and evaluated on the basis of the following criteria.

○‧‧‧No stripping △‧‧‧Checkerboard cut pieces are peeled off 20% or less ╳‧‧‧ checkerboard cut pieces peeled off more than 21%

[Evaluation of Bendingness] The sample B was placed on the outer side of the surface of the hardened coating film, bent by 180 degrees, and the state of the coating film at this time was evaluated on the basis of the following criteria.

○‧‧‧No cracks (cracks) on the membrane surface △‧‧‧ only a few cracks on the membrane surface ╳‧‧‧The membrane is cracked and cracks are clearly visible on the membrane surface.

[Evaluation of developability] With respect to the sample C, development was carried out for 60 seconds at a spray pressure of ² kg/cm ² using a 1% aqueous sodium carbonate solution. The number of stages in which the coating film was wetted through the developing solution was taken as the number of wetted sections, and the number of cleaned portions of the coating film by the developer was taken as the number of peeling sections. The lower the number of peeling sections, the faster the developing speed, and it can be said that the developability is excellent. The number of peeling sections was used, and the developability was judged based on the following criteria.

○‧‧‧Number of stripping segments≦10 △‧‧‧Number of stripping segments = 11~15 ╳‧‧‧ peeling number ≧16

[Analytical evaluation] Regarding the number of wet sections and the number of peeling sections confirmed by the developability evaluation, the following The equation is used to find the analytical step difference.

[Analysis step difference]=[Number of stripping segments]-[Number of wet segments]

The smaller the analysis step is, the more vivid the pattern can be formed in the actual pattern forming step, and it can be said that the resolution is excellent. This analysis step is used, and the analyticity is judged based on the following criteria.

○‧‧‧Analysis of the difference ≦2 △‧‧‧analysis step difference=3~5 ╳‧‧‧analysis of the difference of 6

<Results of Evaluation 1> The results of Evaluation 1 are shown in Table 3.

As a result of the evaluation 1, it can be known that, in the prior art (Comparative Examples 1 to 5), the excellent adhesion/flexibility is poor in developability/analysis, and Those who have excellent image/resolution are poor in adhesion/bending. On the other hand, the resin compositions (Examples 1 to 13) of the present invention are excellent in balance of physical properties such as adhesion, flexibility, developability, and analytical property.

[Embodiment 14]

100.0 parts of a resin varnish (a solution of a carboxyl group-containing urethane prepolymer) obtained in Production Example 1 as a photopolymerization initiator 2-methyl-1-[4-(methylthio)benzene Base]-2- Lolinyl-1-propane (IRGACURE-907: manufactured by Chiba Specialty Chemical Co., Ltd.) 2.5 parts, the same 2,4-diethyl 9-oxosulfur (DETX-S: manufactured by Nippon Kayaku Co., Ltd.) 0.25 parts of di-trimethylolpropane tetraacrylate as a compound containing a photosensitive ethylenically unsaturated group (SR-355: manufactured by Nippon Kayaku Co., Ltd.) 7.5 parts of hydrogenated bisphenol A glycidyl ether (Denacol EX-252: manufactured by Nagase Chemtex Co., Ltd.), which is a thermosetting component, was uniformly dissolved and mixed to prepare a photosensitive resin composition of the invention.

[Examples 15 to 26]

The resin varnish obtained in Production Examples 2 to 13 was blended in the same ratio as in Example 14 to prepare a photosensitive resin composition containing each resin.

[Comparative Example 6~10]

The resin varnish obtained in Production Examples 14 to 18 was blended in the same ratio as in Example 14 to obtain a photosensitive resin composition containing each resin.

<Evaluation 2> The following evaluation was performed with respect to the photosensitive resin composition obtained.

[Production of sample D] The processing was carried out in the same manner as in the preparation of Sample A of Evaluation 1, to obtain a dried coating film. Think of this as sample D.

[Production of Sample E] Sample A was used instead of Sample A, and processed in the same manner as in Production Sample B of Evaluation 1, to obtain a cured film. Think of this as sample E.

[Production of sample F] Sample A was used instead of sample A, and processed in the same manner as in the preparation of sample C of Evaluation 1, to obtain a cured film. Think of this as sample F.

[Production of Sample G] The obtained photosensitive resin composition was applied onto a 38 μm thick polyethylene terephthalate (hereinafter referred to as "PET") separation membrane so that the dried film thickness was 20 μm. After drying at 80 ° C in a hot air dryer for 30 minutes, it was cooled to room temperature. Then, ultraviolet rays having a cumulative light amount of 300 mJ/cm ² were irradiated by an ultraviolet exposure apparatus in the same manner as the user of the sample B of Evaluation 1, and then subjected to thermal curing (post-hardening) for 1 hour using a hot air dryer at 150 °C. The obtained cured film was cooled to room temperature, and the cured coating film was peeled off from the separation film. Think of this as sample G.

[Evaluation of finger touch viscosity] For the sample D, the following viscosity evaluation was performed by finger touch.

○‧‧‧No fingerprints at all △‧‧‧A little fingerprint appears ╳‧‧‧Significant fingerprints appear

[Evaluation of adhesion] Sample B was replaced with sample E, and the adhesion test was conducted in the same manner as in Evaluation 1, and evaluated.

[Evaluation of Bendingness] Sample B was used instead of sample B, and the bending test was conducted in the same manner as in Evaluation 1, and evaluated.

[Evaluation of developability] Sample C was used instead of sample C, and the developability test was carried out in the same manner as in Evaluation 1, and evaluated on the basis of the following criteria.

○‧‧‧Number of stripping sections≦7 △‧‧‧Number of stripping segments=8~14 ╳‧‧‧ peeling number ≧15

[Analytical evaluation] The analytical evaluation was performed on the basis of the following criteria in the same manner as in Evaluation 1.

○‧‧‧Analysis of the difference ≦3 △‧‧‧analysis step difference=4~7 ╳‧‧‧Analysis of the difference of 8

[Evaluation of Solvent Resistance] Sample E was immersed in isopropanol for 30 minutes at room temperature. After confirming that there was no abnormality in appearance, the peeling test of the adhesive tape [Scotch tape (registered trademark)] was carried out, and evaluation was performed based on the following criteria.

○‧‧·The appearance of the film is not abnormal, and there is no swelling or peeling. △‧‧‧ at the end of the coating film (the boundary between the coated portion and the polyimide substrate) Some peeling ╳‧‧‧Expansion or peeling on the film

[Evaluation of acid resistance] Sample E was immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there was no abnormality in appearance, the peeling test of the adhesive tape [Scotch tape (registered trademark)] was carried out, and evaluation was performed based on the following criteria.

○‧‧·The appearance of the film is not abnormal, and there is no swelling or peeling. △‧‧‧At the end of the coating film (the boundary between the coated part and the polyimide substrate), there is some expansion or peeling ╳‧‧‧Expansion or peeling on the film

[Evaluation of substrate anti-warping] The sample E was cut into a square of 5 cm × 5 cm, and the surface of the hardened coating film was placed on top, and placed on a flat table at 25 ° C and a humidity of 50% for 12 hours. For the sample after standing, the height of the four corners of the square from the table was measured, and the average value was calculated and evaluated on the basis of the following criteria. The smaller the value, the less the backlash is, indicating good.

○‧‧‧5mm or less △‧‧‧6mm or more~10mm or less ╳‧‧11mm or more

[Evaluation of Flexibility] The sample G was bent 180 degrees and the opposite side of the same portion was also bent 180 degrees. The state of the coating film at this time was judged based on the following criteria.

○‧‧‧No cracks (cracks) on the membrane surface △‧‧‧ only a few cracks on the membrane surface ╳‧‧‧The membrane is cracked and cracks are clearly visible on the membrane surface.

<Evaluation Results> The results of Evaluation 2 are shown in Table 4.

As a result of the evaluation 2, it is understood that the resin composition of the present invention (Examples 14 to 26) is the same as the evaluation 1, and is excellent in adhesion, flexibility, and developability, and has less wrinkles in the dried coating film, so that the workability is superior. . Even the combination of the resistance of the coating film and the anti-warping property or the flexibility of the substrate has a flexible function, and has a function which cannot be achieved by the prior art (Comparative Examples 6 to 10).

[Example 27]

105 parts of a resin varnish (a solution of a carboxyl group-containing urethane prepolymer) obtained in Production Example 1 as a photopolymerization initiator 2-methyl-1-[4-(methylthio)benzene Base]-2- Lolinyl-1-propane (IRGACURE-907: manufactured by Chiba Specialty Chemical Co., Ltd.) 6 parts, the same 2,4-diethyl 9-oxosulfur (DETX-S: manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane PO modified triacrylate (ARONIX M310: manufactured by Toagosei Co., Ltd.) as a compound containing a photosensitive ethylenically unsaturated group 8 parts, a dicyclopentadiene type epoxy (HP7200: manufactured by Dainippon Ink Co., Ltd.) as a thermosetting component, and a diamine diamine as a thermosetting auxiliary (DICY7: Ajinomoto exquisite technology) 1 part, a hydrophobic cerium oxide microparticle as an additive (R812: manufactured by AEROSIL Co., Ltd., Japan), 8 parts, green paste (green pigment / base resin (phenol resin) / solvent (carbitol acetate) ) = 28/12/60) Two parts were prepared and mixed with three rollers to make the photosensitive solder resist ink of the invention.

[Examples 28 to 39]

The resin varnish obtained in Production Examples 2 to 13 was blended in the same ratio as in Example 27 to prepare a solder resist ink containing each resin.

[Comparative Examples 11 to 15]

The resin varnish obtained in Production Examples 14 to 18 was blended in the same ratio as in Example 27 to prepare a solder resist ink containing each resin.

[Embodiment 40]

105 parts of a resin varnish (a solution of a carboxyl group-containing urethane prepolymer) obtained in Production Example 1 as a photopolymerization initiator 2-methyl-1-[4-(methylthio)benzene Base]-2- Lolinyl-1-propane (IRGACURE-907: manufactured by Chiba Specialty Chemical Co., Ltd.) 6 parts, the same 2,4-diethyl 9-oxosulfur (DETX-S: manufactured by Nippon Kayaku Co., Ltd.), trimethylolpropane PO modified triacrylate (ARONIX M310: manufactured by Toagosei Co., Ltd.) as a compound containing a photosensitive ethylenically unsaturated group 8 parts, 25 parts of a flexible epoxy resin (EPICLON EXA-4850-150: manufactured by Dainippon Ink Co., Ltd.) as a thermosetting component, and diamine diamine as a thermosetting auxiliary (DICY7: Ajinomoto 1 part, made of hydrophobic cerium oxide microparticles (R812: manufactured by Japan AEROSIL Co., Ltd.), 8 parts of green paste (green pigment / base resin (phenol resin) / solvent (carbitol) Acetate) = 28/12/60) 2 parts and phosphorus-nitrogen-based flame retardant (SPB-100: manufactured by Otsuka Chemical Co., Ltd.) 8 parts, melamine polyphosphate (PHOSMEL-100: manufactured by Nissan Chemical Industry Co., Ltd.) 8 parts of melamine cyanurate flame retardant (STABIACE MC-5S: manufactured by Nippon Chemical Industry Co., Ltd.) were mixed, and kneaded by three rollers to make a photosensitive solder resist ink of the invention.

[Examples 40 to 52]

The resin varnish obtained in Production Examples 2 to 13 was blended in the same ratio as in Example 40 to prepare a photosensitive solder resist ink containing each resin.

[Comparative Examples 16 to 20]

The resin varnish obtained in Production Examples 14 to 18 was blended in the same ratio as in Example 40 to prepare a photosensitive solder resist ink containing each resin.

<Evaluation 3> The obtained photosensitive solder resist ink was evaluated as described below.

[Production of sample H] The photosensitive solder resists obtained in Examples 21 to 40 and Comparative Examples 11 to 20 were coated on a peeling surface of a 38 μm-thick separation PET film which was subjected to a peeling treatment on one side, and the film thickness after drying was 20 μm. The ink was dried by hot air drying at 80 ° C for 20 minutes. Next, a dry film type photosensitive solder resist having a photosensitive resin composition sandwiched between PET films on both sides was bonded by bonding a photosensitive resin composition on the film and a PET film having a thickness of 25 μm.

Next, the PET film is peeled off from the dry film to expose the surface of the photosensitive resin composition surface and the copper foil surface of the copper-clad laminate (which is subjected to roughening of the copper surface by etching), by vacuum The laminator (60 ° C, 0.2 MPa = 2 Kg / cm ² ) was brought into close contact. Next, a negative film having a resist pattern [ψ70 μm hole, 21 steps, solid line/space = 100/60 (μm/μm)] was adhered to the PET film, and an ultraviolet exposure apparatus (EXM manufactured by ORC) was used. -1201F, short arc lamp) to illuminate ultraviolet rays (400 mJ/cm ² ). Further, the PET film was peeled off, and development was carried out for 60 seconds under a spray pressure of ² kg/cm ² using a 1% aqueous sodium carbonate solution. Thereafter, the film was heat-hardened by a hot air dryer at 150 ° C for 1 hour to prepare a sample H.

[Evaluation of Solvent Resistance] The sample E was replaced with the sample H, and the solvent resistance test was conducted in the same manner as in the evaluation 2, and evaluated.

[Evaluation of acid resistance] Sample H was used instead of sample F, and the acid resistance test was conducted in the same manner as in Evaluation 2 and evaluated.

[Evaluation of developability] Sample C was used instead of sample C, and the developability test was carried out in the same manner as in Evaluation 1, and evaluated on the basis of the following criteria.

○‧‧‧Number of stripping segments≦5 △‧‧‧Number of stripping segments=6~10 ╳‧‧‧ peeling number ≧11

[Analytical evaluation] With respect to the sample H, the ψ70 μm hole portion was observed with a magnifying glass, and the diameter at which the resistive layer was developed to expose the copper surface portion (opening portion) was measured, and the resolution was judged by the following criteria. When the diameter of the hole is closer to 70 μm, the pattern is formed more accurately, and it can be said that the shape is excellent.

○‧‧‧A diameter of 60μm or more △‧‧‧Diameter 40μm or more to 59μm or less ╳‧‧‧39mm below diameter

[Evaluation of solder heat resistance] A rosin-based flux (SPEEDY FLUX P-550-5, manufactured by ASAHI Chemical Research Co., Ltd.) was applied to the sample H, and immersed in a 260 ° C solder bath (JIS C 6481) for 10 seconds. This was regarded as a cycle, and two cycles were repeated, and the state of the film was judged as follows.

○ ‧ ‧ The appearance of the coating film was not abnormal, and there was no swelling or peeling. △‧‧‧ There is local swelling or peeling on the coating film. ╳‧‧·The film is swelled or peeled as a whole.

[Production of Sample I] The photosensitive solder resist inks obtained in Examples 27 to 52 and Comparative Examples 11 to 20 were applied onto a 38 μm-thick separation PET film at a dry film thickness of 20 μm, and at 80 ° C. The hot air dryer was allowed to dry for 20 minutes. Next, in the same manner as the user who produced the sample H in Evaluation 3, the ultraviolet light having a cumulative light amount of 400 mJ/cm ^{2 was} irradiated by an ultraviolet exposure apparatus, and then thermally cured by a hot air dryer at 150 ° C for 1 hour. The obtained cured film was cooled to room temperature, and the cured coating film was peeled off from the separation membrane. Think of this as sample I.

[Evaluation of Flexibility] The flexibility test was conducted for the sample I and evaluated in the same manner as the flexibility evaluation of the evaluation 2.

[Production of sample J] The photosensitive solder resist inks obtained in Examples 40 to 52 and Comparative Examples 16 to 20 containing a flame retardant were irradiated with ultraviolet rays (full surface exposure) without using a negative film having an impedance pattern in the preparation step of the sample H. In the same manner as in the case of the sample H, the sample J was produced.

[Evaluation of flame retardancy] For the sample J, the flame retardancy evaluation according to the UL Subject 94V method was performed, and the results were judged based on the following criteria.

○‧‧‧VTM-0 △‧‧‧VTM-1 ╳‧‧‧VTM-2 or less (including complete combustion, etc.)

<evaluation result> The results of Evaluation 3 are shown in Tables 5 and 6.

As is clear from Table 5, in Comparative Examples 11 and 12 (prior art), although the coating film resistance, developability, and heat resistance are excellent, it is not satisfactory as a flexible insulating protective film used for a flexible printed wiring board or the like. The most important flexibility. Further, in Comparative Examples 13 to 15 (prior art), the film was excellent in flexibility and the film resistance and developability were not good. On the other hand, the photosensitive resin composition of the present invention (Examples 27 to 39) can satisfy all of the physical properties necessary for the flexible insulating protective layer at a high level.

In particular, the carboxyl group-containing photosensitive urethane resin of the present invention which does not have an ester skeleton derived from the half esterification caused by an acid anhydride in the main chain is chemically stable in the main chain, and thus is the same as the same amino carboxylic acid In comparison with Comparative Example 14 or 15 of the ester main skeleton, particularly excellent coating film resistance and heat resistance were maintained, and adhesion and flexibility peculiar to the urethane resin were exhibited. feature. Further, since the carboxyl group-containing photosensitive urethane resin of the present invention has a photosensitive group and a carboxyl group in the side chain, even when the carboxyl group-containing amount is small, excellent developability can be exhibited, and When the side chain functional group is directly bonded to the main chain, since the reactivity is rich, excellent resolution and coating film resistance can be exhibited.

As is clear from the results of Table 6, the physical properties of the prior art (Comparative Examples 16 to 20) as a resist agent were lowered by the addition of the flame retardant, and the photosensitive resin composition of the present invention (Examples 40 to 52) was able to It is both flame retardant and other physical properties as a resisting agent. As described above, the carboxyl group-containing photosensitive urethane resin of the present invention has a photosensitive group and a carboxyl group which are rich in reactivity in the side chain, so that the developability is remarkably hindered even in the presence of a flame retardant. And the elements of photosensitivity, still have excellent developability, It exhibits photosensitivity and maintains clarability and film resistance to exhibit flame retardancy.

The present invention has been described above in terms of specific aspects, and those skilled in the art will recognize that such changes and modifications are within the scope of the invention.

Claims (11)

A photosensitive resin composition containing a carboxyl group-containing photosensitive urethane resin (A), a photopolymerization initiator (B), and a photosensitive ethylenically unsaturated group-containing compound (C), which are characterized The photosensitive urethane resin (A) containing a carboxyl group is a resin produced by polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in a molecule, and a diisocyanate compound ( g) reacting as an essential component to form a carboxyl group-containing ethyl carbamate prepolymer (a); and obtaining a carboxyl group in the carboxyl group-containing ethyl carbamate prepolymer (a), and having an epoxy group Or an oxocyclobutane group is reacted with an epoxy group or an oxocyclobutane group in the ethylenically unsaturated group compound (b) to form a hydroxyl group-containing ethyl carbamate prepolymer (c); The hydroxyl group in the obtained hydroxyl group-containing ethyl carbamate prepolymer (c) is reacted with an acid anhydride group in the acid anhydride group-containing compound (d). The photosensitive resin composition of claim 1, wherein the thermosetting compound (D) is further contained. The photosensitive resin composition of claim 2, further comprising a thermosetting auxiliary (E). The photosensitive resin composition of the first aspect of the invention, wherein the carboxyl group-containing photosensitive urethane resin (A) has an acid value of 10 to 200 mgKOH/g. The photosensitive resin composition of claim 1, wherein the ethylenically unsaturated group of the carboxyl group-containing photosensitive urethane resin (A) The equivalent system is 200~3000g/eq. The photosensitive resin composition of the first aspect of the invention, wherein the carboxyl group-containing photosensitive urethane resin (A) has a weight average molecular weight of 1,000 to 100,000. The photosensitive resin composition of the second aspect of the invention, wherein the thermosetting compound (D) is a compound (k) having two or more epoxy groups or oxocyclobutane groups. A cured product obtained by curing a photosensitive resin composition of the first application of the patent application. A photosensitive solder resist ink comprising the photosensitive resin composition of the first application of the patent scope and a flame retardant. A dry film type photosensitive solder resist characterized by comprising a photosensitive resin composition of the first application of the patent scope and a flame retardant. A method for producing a photosensitive urethane resin containing a carboxyl group, characterized by comprising: a first step of polymer polyol (e), a carboxylic acid compound having two hydroxyl groups in a molecule (f) , the diisocyanate compound (g) is reacted as an essential component to obtain a carboxyl group-containing ethyl carbamate prepolymer (a); and the second step is to carry out the above carboxyl group-containing ethyl carbamate prepolymer (a) reacting an epoxy group or a cyclobutane alkyl group with an ethylenically unsaturated group (b) to obtain a hydroxyl group-containing ethyl carbamate prepolymer (c); and a third step, This is carried out by reacting the above-mentioned hydroxyl group-containing ethyl carbamate prepolymer (c) with the acid anhydride group-containing compound (d).