JP5298855B2 - Photosensitive resin composition and cured product thereof, and method for producing photosensitive resin - Google Patents

Abstract

Disclosed is 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). This photosensitive resin composition is characterized in that the carboxyl group-containing photosensitive urethane resin (A) is a resin obtained by reacting a hydroxy group in a hydroxy group-containing urethane prepolymer (c) with an acid anhydride group in an acid anhydride group-containing compound (d). The hydroxy group-containing urethane prepolymer (c) is obtained by reacting a carboxyl group in a carboxyl group-containing urethane prepolymer (a), which is obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxy groups in a molecule and a diisocyanate compound (g) as essential ingredients, with an epoxy group or an oxethane group in a compound (b) having an epoxy group or an oxethane group and an ethylenically unsaturated group. This photosensitive resin composition is excellent in sensitivity to an active energy ray and enables to form a fine pattern. A cured coating film of the photosensitive resin composition is excellent in flexibility, insulating property, adhesion, solder heat resistance, coating film resistance and flame retardance, and is thus suitably used for a photosolder resist.

Description

  The present invention relates to a photosensitive resin composition containing a carboxyl group-containing photosensitive urethane resin useful for printed wiring boards and the like, a cured product thereof, and a method for producing the photosensitive resin. More specifically, it is useful as a solder resist for flexible printed wiring boards, plating resists, interlayer electrical insulation materials for multilayer printed wiring boards, photosensitive optical waveguides, etc. Photosensitive resin composition containing a specific carboxyl group-containing photosensitive urethane resin, and a cured product thereof, which gives a cured product having excellent properties (flexibility), solder heat resistance, chemical resistance, electrical insulation, etc. The present invention relates to a method for producing a functional resin. Furthermore, the present invention relates to a highly flame-retardant photosensitive solder resist ink and a dry film type photosensitive solder resist containing the photosensitive resin composition.

  In the soldering process that is performed when protecting the wiring (circuit) pattern formed on the board from the external environment or when mounting electronic components on the printed wiring board, solder does not adhere to unnecessary parts. In order to protect the printed wiring board, a protective layer called a coverlay or a solder mask is coated on the printed wiring board. In particular, a protective layer used for a wiring pattern formed on a polyimide film, called a flexible printed wiring board, is required to have adhesion with polyimide, flexibility, and folding resistance.

  Conventionally, as a protective layer for flexible printed wiring boards, a polyimide film called a coverlay film is made by punching a mold that matches the pattern and then pasted using an adhesive, or by thermosetting applied by screen printing There are various types of inks, but for high density and high definition accompanying recent advances in electronics, UV curable photoresist type solder resist ink or dry film type solder resist that can be patterned with higher precision is available. It is being considered.

  In general, in the photo solder resist for flexible printed wiring boards, the photo solder resist conventionally used for rigid substrates can provide pattern accuracy, but the cured coating film is hard and has good adhesion to polyimide. Unfortunately, there was a problem that sufficient flexibility, flexibility and folding resistance could not be obtained.

  In recent years, many proposals have been made as flexible photo solder resists. For example, a resist ink composition is disclosed that includes a resin obtained by reacting succinic anhydride with an addition product of an epoxy resin having a bisphenol A skeleton in the main chain and an unsaturated group-containing monocarboxylic acid (Patent Document 1). ). Although this is excellent in developability, photosensitivity, adhesion, heat resistance, etc., there is a problem that flexibility and folding resistance are still insufficient. Further, as a photosensitive thermosetting composition, a reaction product of a secondary hydroxyl group generated by an esterification reaction of a cresol novolak type epoxy compound and an unsaturated monocarboxylic acid and a saturated or unsaturated polybasic acid anhydride, A reaction product of the secondary hydroxyl group and an unsaturated group-containing isocyanate compound has been proposed (Patent Document 2). Although these are very excellent in adhesion, solder heat resistance, and coating film resistance, there is a problem that flexibility and folding resistance are still insufficient.

  In addition, a photosensitive element containing a polymer obtained by copolymerizing a monomer containing (meth) acrylic acid and a (meth) acrylic acid ester as a binder component has been proposed (Patent Document 3). These are excellent in developability and resolution, but when used in flexible printed wiring board applications, sufficient adhesion, flexibility and folding resistance cannot be obtained.

  Also, a carboxyl group-containing polyester polyol having an ester bond derived from half-esterification in the main chain is produced by reacting a polyol compound with a polybasic acid anhydride having two acid anhydride groups in the molecule. This is reacted with a polyisocyanate compound to obtain a carboxyl group-containing urethane prepolymer, and further has one epoxy group in the molecule with respect to a part of the carboxyl groups in the urethane prepolymer (meth). A photosensitive resin composition containing a carboxyl group-containing urethane oligomer obtained by reacting acrylate has been proposed (Patent Document 4). Although these are flexible, they have an ester bond derived from half-esterification with a polybasic acid anhydride in the main chain, so that the dehydration occurs at high temperatures and the main chain is easily cleaved. It has a stable structure, and since the carboxyl group is directly connected to the main chain, the mobility of the carboxyl group is suppressed, so that sufficient developability, various coating film resistance, and solder heat resistance are sufficient. It was not something.

  Moreover, the photosensitive resin composition which added the phosphorus flame retardant is disclosed (patent document 5). In order to reduce the burden on the environment, these are made flame retardant by using a non-halogen flame retardant. However, in order to give sufficient flame retardancy with a non-halogen flame retardant, it is necessary to add a large amount of flame retardant, and because of this, the resolution in the order of several tens of μm, which has been demanded in recent years, is required. Since the physical properties other than the flame retardancy required for the resist are lowered, such as a significant decrease, it is not sufficient to achieve both the flame retardancy and other physical properties.

  As described above, the conventional technology has both sufficient flexibility and folding resistance required as a protective layer for a flexible printed wiring board and developability and solder heat resistance capable of realizing high-precision patterning, and A resin composition that can satisfy all physical properties such as electrical insulation, chemical resistance, and flame retardancy necessary as a protective layer for a circuit and a cured product thereof have not been obtained.

Printed wiring boards are required to have high precision and high density in order to reduce the size and weight of portable devices and improve communication speed. Flexible printed wiring used mainly in the bent and connected areas of devices. The trend is the same for boards. Against this background, demands for protective layers for flexible printed wiring boards are becoming more and more advanced, and developability that can achieve higher definition of resist patterns and higher flexibility than conventional requirements. Performance that satisfies solder heat resistance, substrate adhesion, high insulation, coating film resistance, flame retardancy, etc. is required while maintaining the properties and folding resistance. Currently, commercially available photo solder resists cannot sufficiently meet these requirements.
Japanese Patent No. 3281473 Japanese Patent No. 2707495 JP 2004-279479 A JP 2001-159815 A JP 2006-251715 A

  The present invention has excellent photosensitivity to active energy rays, and can form a fine pattern by developing with a dilute alkaline aqueous solution. The cured coating film obtained through a post-curing (post-cure) process is flexible, insulating, and adhesive. An object of the present invention is to provide a photosensitive resin composition that is excellent in solder heat resistance, coating film resistance, flame retardancy, etc., and that is suitably used for a photo solder resist, and a cured product thereof, as well as a method for producing a photosensitive resin. And

  As a result of intensive studies, the present inventors have found that a photosensitive resin composition containing a specific carboxyl group-containing photosensitive urethane resin (A) solves the above-described problems. The present invention has been completed.

That is, the first invention is a photosensitive resin composition comprising a carboxyl group-containing photosensitive urethane resin (A), a photopolymerization initiator (B), and a photosensitive ethylenically unsaturated group-containing compound (C). There,
The carboxyl group-containing photosensitive urethane resin (A)
A carboxyl group in a carboxyl group-containing urethane prepolymer (a) obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components; ,
A hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) obtained by reacting an epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group;
The present invention relates to a photosensitive resin composition, which is a resin obtained by reacting an acid anhydride group in an acid anhydride group-containing compound (d).

  Moreover, 2nd invention is related with the photosensitive resin composition of 1st invention which contains a thermosetting compound (D) further.

  Moreover, 3rd invention is related with the photosensitive resin composition of 2nd invention which contains a thermosetting adjuvant (E) further.

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

  Moreover, 5th invention is related with the photosensitive resin composition of the invention in any one of 1st-4th whose ethylenically unsaturated group equivalent of carboxyl group-containing photosensitive urethane resin (A) is 200-3000 g / eq.

  The sixth invention relates to the photosensitive resin composition according to any one of the first to fifth inventions, wherein the weight average molecular weight of the carboxyl group-containing photosensitive urethane resin (A) is 1000 to 100,000.

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

  The eighth invention relates to a cured product obtained by curing the photosensitive resin composition of any one of the first to seventh inventions.

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

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

Furthermore, the eleventh invention is a carboxyl group-containing urethane obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components. A first step of obtaining a prepolymer (a);
Second step of obtaining a hydroxyl group-containing urethane prepolymer (c) by reacting the carboxyl group-containing urethane prepolymer (a) with a compound (b) having an epoxy group or an oxetane group and an ethylenically unsaturated group. ,
And a method for producing a carboxyl group-containing photosensitive urethane resin, comprising a third step of reacting the hydroxyl group-containing urethane prepolymer (c) with the acid anhydride group-containing compound (d). .

  According to the present invention, it has excellent photosensitivity to active energy rays, and can form a fine pattern by development with a dilute alkaline aqueous solution, and a cured coating film obtained through a post-curing (post-cure) process is flexible, insulating and adhesive It is excellent in solder heat resistance, coating film resistance, flame retardancy, etc., and can provide a photosensitive resin composition suitably used for a photo solder resist and a cured product thereof, and further a method for producing a photosensitive resin. I can do it now. The photosensitive resin composition of the present invention includes a solder resist for flexible printed wiring boards, a photosensitive coverlay film, a plating resist, an interlayer electrical insulating material for wiring boards, a photosensitive optical waveguide, and a silver paste on a polyethylene terephthalate film. It can be suitably used as a coverlay resist for a flexible printed circuit board formed with a circuit by printing a conductive ink such as carbon paste.

  As described above, the carboxyl group-containing urethane oligomer described in Patent Document 4 contains an ester bond derived from half esterification with a polybasic acid anhydride in the main chain, whereas the photosensitive resin of the present invention. Since the composition does not have such an ester bond derived from half esterification in the main chain, the main chain is chemically stable. Even when exposed to high-temperature conditions such as a bath, it exhibits excellent heat resistance and, at the same time, exhibits the adhesion and flexibility specific to urethane resins. In addition, the carboxyl group-containing photosensitive urethane resin (A) of the present invention has a photosensitive group and a carboxyl group in the side chain, so that it exhibits very good developability even when the amount of the carboxyl group is small, Since these side chain functional groups are rich in reactivity compared to the case where they are directly connected to the main chain, they can exhibit excellent photocurability, resolution and coating film resistance. 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 a compound (b) having an epoxy group or an oxetane group and an ethylenically unsaturated group with respect to 1 mol of the carboxyl group in the carboxyl group-containing urethane prepolymer (a). ) Epoxy group or oxetane group is preferably reacted in a proportion of 0.1 mol to 1.0 mol, more preferably in a proportion of 0.30 mol to 0.95 mol, to give a hydroxyl group-containing urethane prepolymer (c). After the production, the ratio of the acid anhydride group in the acid anhydride group-containing compound (d) to the hydroxyl group in 1 mol of the hydroxyl group-containing urethane prepolymer (c) is preferably 0.1 mol to 1.0 mol. More preferably, it can be obtained by reacting at a ratio of 0.30 mol to 0.95 mol.
The molar ratio is a reaction molar ratio, and each starting material is used in an amount that enables the reaction at the molar ratio. Therefore, for example, the “carboxyl group-containing urethane prepolymer (a)” and the “compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group” are combined with the “carboxyl group-containing urethane prepolymer”. The epoxy group or oxetane group in the “compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group” is 0.1 mol to 1.2 mol per 1 mol of the carboxyl group in the “polymer (a)”. May be reacted in molar amounts. Moreover, the description regarding the reaction molar ratio in this specification is the same meaning as the above.

Here, with respect to the carboxyl group in the carboxyl group-containing urethane prepolymer (a), the ratio of reacting the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group, When the amount is less than 0.1 mol, the amount of unsaturated groups in the finally obtained carboxyl group-containing photosensitive urethane resin (A) decreases, and it is difficult to obtain desired photosensitivity in the photosensitive resin composition.
In addition, with respect to 1 mol of carboxyl groups in the carboxyl group-containing urethane prepolymer (a), 1.0 mol of epoxy groups or oxetane groups in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group is used. A larger amount cannot be reacted.

Furthermore, when the ratio of the acid anhydride group in the acid anhydride group-containing compound (d) to react with 1 mol of the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) is less than 0.1 mol, a carboxyl group The ratio of introducing the amount is reduced, and it is difficult to obtain desired developability in the photosensitive resin composition.
In addition, the acid anhydride group in the acid anhydride group-containing compound (d) cannot be reacted in an amount greater than 1.0 mol with respect to 1 mol of the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c).

  The carboxyl group-containing urethane prepolymer (a) is produced by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components. Is done. Further, as a desired component, a hydroxyl group-containing compound (h) [excluding the “polymer polyol (e)” and the “carboxylic acid compound (f) having two hydroxyl groups in the molecule”) and an isocyanate in the molecule An isocyanate compound (i) having one or more groups and an amine compound (j) can be appropriately used.

  In the present invention, when synthesizing the carboxyl group-containing urethane prepolymer (a), the ratio of the reaction of the starting material is polymer polyol (e), carboxylic acid compound (f) having two hydroxyl groups in the molecule, In addition, regarding the hydroxyl group-containing compound (h) and the amine compound (j) that are optionally added, when the total of the hydroxyl group and amino group contained in these is 1 mol, an isocyanate group is present in the diisocyanate compound (g) and the molecule. The total of isocyanate groups contained in the isocyanate compound (i) having one or three or more is preferably reacted in a proportion of 0.50 mol to 1.00 mol, and a proportion of 0.70 mol to 0.95 mol It is more preferable to make it react with. When the isocyanate group is less than 0.50 mol, the molecular weight of the carboxyl group-containing urethane prepolymer (a) becomes small, and it becomes difficult to obtain desired coating film resistance and film formability. Moreover, when there are more isocyanate groups than 1.00 mol, an excess isocyanate group remains in a system, and it is easy to produce the problem that a by-product generate | occur | produces in the subsequent reaction process or gelatinizes during reaction.

  At this time, the polymer polyol (e), the carboxylic acid compound (f) having two hydroxyl groups in the molecule, the hydroxyl group-containing compound (h) optionally added, and the amine compound (j) are finally obtained. It is preferable to add a carboxylic acid compound (f) having two hydroxyl groups in the molecule at a rate such that the resulting carboxyl group-containing urethane prepolymer (a) has an acid value of 5 to 200 mgKOH / g (more preferably 10-180 mg KOH / g).

The polymer polyol (e) used in the present invention is a compound containing two or more hydroxyl groups, and preferably has a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (hereinafter also referred to as “GPC”) of 500. ~ 50,000 compounds. In the present specification, unless otherwise specified, the weight average molecular weight means a polystyrene equivalent weight average molecular weight by GPC measurement. In the present invention, as the polymer polyol (e), polyethylene oxide, polypropylene oxide, block copolymer or random copolymer of ethylene oxide / propylene oxide, polytetramethylene glycol, block copolymer of tetramethylene glycol and neopentyl glycol are used. Polyether polyols such as polymers or random copolymers;
Polyester polyols which are condensates of polyhydric alcohols or polyether polyols with polybasic acids such as maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, isophthalic acid;
Polycarbonate polyols obtained by reaction of glycol or bisphenol with a carbonic acid ester or reaction of phosgene with glycol or bisphenol in the presence of alkali;
Examples thereof include caprolactone-modified polyol such as caprolactone-modified polytetramethylene polyol, polyolefin polyol, polybutadiene polyol such as hydrogenated polybutadiene polyol, and polyol such as silicone polyol. In the present invention, these polymer polyols (e) may be used alone or in combination.

  Among these, polyether polyols such as polytetramethylene glycol, block copolymer of tetramethylene glycol and neopentyl glycol or random copolymer are excellent in flexibility, hydrolysis resistance, and hydrophilicity of the skeleton. When used in the invention, the coating film has excellent flexibility, chemical resistance, developability and the like, and is particularly preferable.

The “carboxylic acid compound (f) having two hydroxyl groups in the molecule” used in the present invention is a compound having two hydroxyl groups and one or more (preferably 1 to 3) carboxyl groups in the molecule. A compound having a weight average molecular weight of preferably 90 to 1000, for example, dimethylolbutanoic acid, dimethylolpropionic acid, and derivatives thereof (caprolactone adduct, ethylene oxide adduct, propylene oxide adduct, etc.), Examples include 3-hydroxysalicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid, 2-carboxy-1,4-cyclohexanedimethanol and the like.
Among these, dimethylolbutanoic acid and dimethylolpropionic acid are preferable in the present invention in that the concentration of carboxyl groups in the resin can be increased. In addition, caprolactone adducts, ethylene oxide adducts, propylene oxide adducts and the like can reduce the amount of urethane bonds in the carboxyl group-containing urethane prepolymer (a), so that the flexibility of the coating film is improved. Can be used in Furthermore, aromatic compounds 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, these carboxylic acid compounds (f) can be appropriately selected and used according to the purpose and application, and may be used alone or in combination. Also good.

  As a diisocyanate compound (g) used by this invention, C4-C50 aromatic diisocyanate, aliphatic diisocyanate, araliphatic diisocyanate, alicyclic diisocyanate etc. can be mentioned, for example.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

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

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1 , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) A cyclohexane etc. can be mentioned.

  In the present invention, aromatic diisocyanate or araliphatic diisocyanate is preferably used to improve the heat resistance of the target photosensitive resin composition, and the flexibility of the target photosensitive resin composition is improved. It is preferable to use aliphatic diisocyanate or alicyclic diisocyanate. In the present invention, these diisocyanate compounds (g) can be appropriately selected and used according to the purpose and application, or only one kind may be used alone or a plurality may be used in combination.

  The hydroxyl group-containing compound (h) used in the present invention is a compound having one or more hydroxyl groups, but the compound belonging to the “polymer polyol (e)” and the “carboxylic acid compound having two hydroxyl groups in the molecule ( f) a compound excluding the compound belonging to “,” and representative examples thereof include, for example, a monoalcohol compound (h1) having one hydroxyl group in the molecule, two hydroxyl groups in the molecule, and a carboxyl group. A diol compound (h2) having a weight average molecular weight of 50 to 499 and a polyhydric alcohol compound (h3) having three or more hydroxyl groups in the molecule and having a weight average molecular weight of 50 to 499. Can do. These may have both a hydroxyl group and a functional group other than a hydroxyl group in the molecule. Moreover, you may use individually and may use it in combination of multiple.

Examples of the monoalcohol compound (h1) having one hydroxyl group in the molecule include aliphatics such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, lauryl alcohol, and stearyl alcohol. Monoalcohol;
Alicyclic monoalcohols such as cyclohexanol;
Aromatic monoalcohols such as benzyl alcohol, fluorenol, phenol, and methoquinone;
Examples of monoalcohol compounds having functional groups other than hydroxyl groups include hydroxyl group-containing carboxylic acid compounds such as 12-hydroxystearic acid, 2-hydroxyethyl (meth) acrylate (“2-hydroxyethyl acrylate” and “2-hydroxyethyl methacrylate” And the like, the same shall apply hereinafter), a hydroxyl group-containing (meth) acrylate compound such as 4-hydroxybutyl (meth) acrylate, a hydroxyl group-containing epoxy compound such as glycidol, Examples include hydroxyl group-containing oxetane compounds such as oxetane alcohol.
Other examples include oligomer-type monoalcohols such as one-end methoxylated polyethylene glycol, one-end methoxylated polypropylene glycol, and caprolactone addition polymer using monoalcohol as an initiator.

  In the present invention, when these monoalcohol compounds are used, since the polymerization terminal of the resulting carboxyl group-containing urethane prepolymer (a) can be sealed, the low molecular weight carboxyl group-containing urethane prepolymer (a) is intentionally produced. Can be suitably used when molecular weight adjustment is required, such as when synthesizing. Moreover, when using the hydroxyl-containing compound which has functional groups other than a hydroxyl group, since a functional group other than a hydroxyl group can be introduce | transduced into the terminal of a carboxyl group-containing urethane prepolymer (a), a carboxyl group-containing urethane prepolymer ( It can be suitably used when terminal modification of a) is required. In the present invention, in consideration of hydroxyl reactivity and polymerization control, lauryl alcohol, stearyl alcohol, cyclohexanol, 12-hydroxystearic acid, glycidol, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Is preferably used.

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, tetraethylene glycol, Propylene glycol, dipropylene glycol, butylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,9- Aliphatic diols such as nonanediol, hydrogenated bisphenol A, 1,4-cyclohexanedimethanol, spiroglycol;
Aromatic diols such as hydroquinone, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, bisphenol, bisphenoxyethanol fluorene, bisphenol fluorene, biscresol fluorene;
N, N-bis (2-hydroxypropyl) aniline, N, N-bis (2-hydroxyethyl) aniline, N, N-bis (2-hydroxyethyl) methylamine, N, N-bis (2-hydroxyethyl) ) Propylamine, N, N-bis (2-hydroxyethyl) butylamine, N, N-bis (2-hydroxyethyl) hexylamine, N, N-bis (2-hydroxyethyl) octylamine, N, N-bis Tertiary amino group-containing diol compounds such as (2-hydroxyethyl) benzylamine and N, N-bis (2-hydroxyethyl) cyclohexylamine;
Other examples include sulfur atom-containing diols and bromine atom-containing diols. In the present invention, these diol compounds (h2) may be used alone or in combination. In the present invention, by using a tertiary amino group-containing diol compound such as N, N-bis (2-hydroxypropyl) aniline, the cohesive force of the coating film is increased, and it is more resistant while maintaining flexibility. It is preferable because a tough coating film having excellent resistance can be formed.

  Examples of the polyhydric alcohol compound (h3) having three or more hydroxyl groups in the molecule and having a weight average molecular weight of 50 to 499 include trimethylolethane, polytrimethylolethane, trimethylolpropane, and polytrimethylolpropane. Pentaerythritol, polypentaerythritol, sorbitol, mannitol, arabitol, xylitol, galactitol, glycerin and the like. In the present invention, when these polyhydric alcohol compounds (h3) are used, a part of the resulting carboxyl group-containing urethane prepolymer (a) can be branched. Resistance can be improved. Therefore, in the present invention, it may be used as necessary for the purpose of further improving the resistance of the cured coating film. Among these polyhydric alcohol compounds (h3), it is preferable to use trimethylolpropane or pentaerythritol in terms of reaction control.

  As the “isocyanate compound (i) having one or more isocyanate groups in the molecule” used in the present invention, specifically, as a monofunctional isocyanate having one isocyanate group in one molecule, ) Acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like. In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Examples of the polyfunctional isocyanate having 3 or more isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. And a trimethylolpropane adduct of diisocyanate (g) described above, a burette reacted with water, and a trimer having an isocyanurate ring.

  In the present invention, when it is desired to reduce the unreacted hydroxyl group remaining at the terminal of the carboxyl group-containing urethane prepolymer (a), a monofunctional isocyanate having one isocyanate group in one molecule is used for the purpose of sealing the terminal. In addition, for the purpose of improving the resistance of a coating film obtained by photocuring from the photosensitive resin composition according to the present invention, or a coating film obtained by photocuring and heat curing, a carboxyl group-containing urethane prepolymer ( When branching a), it is preferable to use a polyfunctional isocyanate having three or more isocyanate groups in one molecule. In the present invention, these isocyanate compounds can be appropriately selected and used according to the purpose and application, and only one kind may be used alone or a plurality may be used in combination.

  Furthermore, in the present invention, when the carboxyl group-containing urethane prepolymer (a) is synthesized, an amine compound (j) can be reacted as a desired component. The amine compound (j) in the present invention refers to a compound having at least one primary or secondary amino group in the molecule.

  Examples of the amine compound (j) of the present invention include monoamine compounds such as propylamine, hexylamine, cyclohexylamine, benzylamine, 2-ethylhexylamine, octylamine, dodecylamine, and aniline, ethylenediamine, propylenediamine, and trimethylene. Diamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine and other aliphatic polyamines, isophoronediamine And cycloaliphatic polyamines such as dicyclohexylmethane-4,4′-diamine and aromatic polyamines such as phenylenediamine and xylylenediamine. .

  Also, diamine compounds such as both-end amino group-modified polyethylene oxide, both-end amino group-modified polypropylene oxide, polysilicone diamine, and polybutadiene diamine, one-end amino group-modified polyethylene oxide, one-end amino group-modified polypropylene oxide, polysilicon monoamine, Examples thereof include monoamine compounds such as polybutadiene monoamine, and polymer type polyamine compounds such as polyethyleneimine and polyallylamine.

  Also, as the amine compound (j), the primary amino group in the compound having a primary amino group is modified to a secondary amino group by Michael addition reaction with the (meth) acrylate group of the (meth) acrylate group-containing compound. The amine compound obtained by doing this is mentioned. When such a compound is used, a polar functional group can be introduced into the carboxyl group-containing urethane prepolymer (a) by devising a (meth) acrylate group-containing compound. For example, the acrylate group of 4-hydroxybutyl acrylate is Michael-added to the primary amino group of isophoronediamine to synthesize a diamine having a secondary amino group and used as a raw material for the urethane resin of the present invention. Hydroxyl groups can be introduced therein.

  In addition, as the amine compound (j) of the present invention, an amine compound having a functional group other than an amino group can also be used. For example, 2-hydroxyethylethylenediamine, N- (2-hydroxyethyl) propylenediamine, (2-hydroxyethylpropylene) diamine, (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, Diamines having a hydroxyl group such as (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine, dimer amine obtained by converting the carboxyl group of dimer acid into an amino group, and polyoxyl having propoxyamine at both ends. Examples thereof include oxyalkylene glycol diamine.

In the present invention, these amine compounds (j) may be used alone or in combination, and a monoamine, a diamine, or a polyamine is appropriately selected or used depending on the purpose or application. be able to.
For example, when a carboxyl group-containing urethane prepolymer (a) is synthesized, a monoamine compound is used in combination, so that the amount of residual isocyanate groups can be reduced and the ends can be sealed, so that the molecular weight can be easily controlled. Moreover, by using a diamine compound, it becomes possible to extend a polymer chain, and a high molecular weight polymer can be obtained. Furthermore, by using a polyamine compound, the polymer chain can be branched to finally improve the cohesive strength / resistance of the coating film.

  As a method of reacting the amine compound (j), a method of reacting with the diisocyanate compound (g) [and optionally further with the isocyanate compound (i)] after charging simultaneously with other raw materials such as the polymer polyol (e), An example is a method of obtaining a carboxyl group-containing urethane prepolymer (a) containing a urea bond by previously synthesizing an isocyanate-terminated urethane chain and adding or dropping the amine compound (j) to extend the chain. It is done. In the present invention, when the amine compound (j) is reacted in this manner, the cohesive force of the resulting carboxyl group-containing photosensitive urethane resin (A) is improved, and a coating film with more excellent heat resistance and durability can be formed. Therefore, the amine compound (j) may be used as necessary.

In the present invention, the synthesis conditions of the carboxyl group-containing urethane prepolymer (a) are not particularly limited, and can be performed under known conditions.
For example, a polymer polyol (e), a carboxylic acid compound (f), and a solvent [and optionally a hydroxyl group-containing compound (h)] are charged into a flask, and heated and stirred at 20 to 120 ° C. under a nitrogen stream uniformly. After dissolution, the diisocyanate compound (g) [and optionally the isocyanate compound (i)] is added and heated at 50 to 150 ° C. with stirring to obtain the carboxyl group-containing urethane prepolymer (a). In this case, a urethanization catalyst such as an organic tin compound or a tertiary amino group-containing compound may be used as necessary.
In addition, before adding the diisocyanate compound (g), the polymer polyol (e), the carboxylic acid compound (f), and the solvent previously charged in the flask are heated and stirred at 100 ° C. or more to remove part of the solvent. May be. This operation is usually performed to remove water in the system (dehydration treatment). By this operation, when the diisocyanate compound (g) is reacted, the deactivation of isocyanate groups by water is suppressed, and finally, Thus, a carboxyl group-containing urethane prepolymer (a) having physical property values closer to theoretical values can be obtained.

  Next, the present invention comprises reacting a carboxyl group-containing urethane prepolymer (a) with a compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group, to thereby produce a hydroxyl group-containing urethane prepolymer (c). Is synthesized.

  In the present invention, the proportion of the carboxyl group-containing urethane prepolymer (a) and the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group is reacted as described above. The epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group is preferably 0.1 mol to 1.0 mol per mol of the carboxyl group in the polymer (a). It is preferable to react at a molar ratio, more preferably at a molar ratio of 0.3 to 0.95 mol.

  Here, with respect to the carboxyl group in the carboxyl group-containing urethane prepolymer (a), the ratio of reacting the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group, When the amount is less than 0.1 mol, the amount of unsaturated groups in the finally obtained carboxyl group-containing photosensitive urethane resin (A) is small, and thus it is difficult to obtain desired photosensitivity in the photosensitive resin composition.

  The compound (b) having “epoxy group or oxetane group and ethylenically unsaturated group” used in the present invention is preferably a compound having 6 to 50 carbon atoms, such as glycidyl (meth) acrylate, glycidyl cinnamic acid, 4 -Hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4-vinyl-1-cyclohexene -1,2-epoxide, 1,3-butadiene monoepoxide, oxetanyl (meth) acrylate, oxetanyl cinnamic acid, and hydroxyl group of a hydroxyl group-containing polyfunctional acrylic monomer such as pentaerythritol triacrylate Sensuality Rate group-containing monoepoxides and polyfunctional acrylate groups that are obtained by modifying most of the epoxy groups of phenol novolac-type epoxy resins to acrylate groups with acrylic acid, etc., leaving one epoxy group per molecule on average Monoepoxide, polyfunctional acrylate group-containing monoepoxide obtained by reacting a part of the epoxy group of a compound having two or more epoxy groups in the molecule with the carboxyl group of the carboxyl group-containing polyfunctional acrylic monomer By reacting these epoxy groups or oxetane groups with carboxyl groups in the urethane prepolymer (a), a hydroxyl group-containing urethane prepolymer (c) is obtained.In the present invention, the epoxy group or oxetane group and ethylene are obtained. The compound (b) having a polymerizable unsaturated group is only one kind It may be used alone or in combination of two or more.

  Among them, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like are rich in reactivity with the carboxyl group in the carboxyl group-containing urethane prepolymer (a) in the present invention, and the resulting photosensitivity. The photosensitive resin composition is particularly preferable because it is very excellent in photosensitivity.

In the present invention, “compound (o) having no ethylenically unsaturated group and having an epoxy group or oxetane group” is referred to as “compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group”. Can also be used in combination. The “compound (o) having no ethylenically unsaturated group and having an epoxy group or oxetane group” which can be optionally used in the present invention is preferably a compound having 6 to 50 carbon atoms, such as 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, stearyl glycidyl ether, allyl glycidyl ether, glycidol N-glycidyl phthalimide, 1,3-dibromophenyl glycidyl ether, Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.), oxetane alcohol and the like.
In the present invention, these “compounds (o) having no ethylenically unsaturated group and having an epoxy group or oxetane group” are “compounds (b) having an epoxy group or oxetane group and an ethylenically unsaturated group”. By using together, it is possible to control the photosensitivity of the carboxyl group-containing photosensitive urethane resin (A) of the present invention more widely, so that it is preferably used as appropriate according to the purpose and application.

  The reaction conditions for reacting the carboxyl group in the carboxyl group-containing urethane prepolymer (a) with the epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group are as follows: It is not specifically limited, It can carry out on well-known conditions. For example, a carboxyl group-containing urethane prepolymer (a), an epoxy group or a compound (b) having an oxetane group and an ethylenically unsaturated group in the flask [and optionally “having no ethylenically unsaturated group, epoxy group or A compound (o) having an oxetane group]]] and a solvent are charged, and heated at 50 to 150 ° C. with stirring in an oxygen stream to obtain a hydroxyl group-containing urethane prepolymer (c). At this time, it is preferable to add a tertiary amino group-containing compound such as triethylamine or dimethylbenzylamine as a catalyst, and to add a polymerization inhibitor of an ethylenically unsaturated group such as hydroquinone or methoquinone. The addition amount of the catalyst is 0.1 to 10% by weight with respect to the total of (a) and (b), and the addition amount of the inhibitor is 0.05 to 10% by weight. preferable.

Furthermore, in this invention, when manufacturing carboxyl group-containing photosensitive urethane resin (A), a hydroxyl-containing urethane prepolymer (c) and an acid anhydride group containing compound (d) are made to react. . The acid anhydride group-containing compound (d) used in the present invention is a compound having an acid anhydride group, and by reacting the acid anhydride group with a hydroxyl group in the hydroxyl group-containing urethane prepolymer (c), the present invention. The carboxyl group-containing photosensitive urethane resin (A) is obtained.
In the present invention, the proportion of the hydroxyl group-containing urethane prepolymer (c) and the acid anhydride group-containing compound (d) to be reacted is an acid anhydride group with respect to 1 mol of the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c). The acid anhydride group in the containing compound (d) is reacted at a ratio of 0.1 mol to 1.0 mol.
When the ratio of reacting the acid anhydride group in the acid anhydride group-containing compound (d) with respect to 1 mol of the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) is less than 0.1 mol, curability and development The ratio of introducing a carboxyl group having excellent properties is reduced, 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 1 or 2 carboxylic acid anhydride groups in the molecule and having 4 to 50 carbon atoms. Acid, trimellitic anhydride, methyltetrahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methylpentahydrophthalic anhydride, methyltrihydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, Examples thereof include compounds containing an acid anhydride group having an alicyclic structure such as methylcyclohexene dicarboxylic acid anhydride, het acid anhydride, tetrabromophthalic anhydride, or an aromatic ring structure. Other acid anhydride group-containing compounds (d) include succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl Maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride, butyl glutamic anhydride, hexyl glutamic anhydride, heptyl glutamic anhydride, Examples include octyl glutamic anhydride, decyl glutamic anhydride, dodecyl glutamic anhydride, and the like. In the present invention, the acid anhydride group-containing compound (d) may be used alone or in combination.

  Among these, succinic anhydride, tetrahydrophthalic anhydride, and the like are particularly preferable because the photosensitive resin composition obtained in the present invention has excellent developability, pattern formability, and coating film resistance.

  The reaction conditions for reacting the hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) with the acid anhydride group in the acid anhydride group-containing compound (d) are not particularly limited, and are performed under known conditions. Can do. For example, a hydroxyl group-containing urethane prepolymer (c), an acid anhydride group-containing compound (d), and a solvent are charged into a flask, and heated at 50 to 150 ° C. with stirring in an oxygen stream, thereby causing carboxyl group-containing photosensitive urethane. Resin (A) is obtained. At this time, it is preferable to add a tertiary amino group-containing compound such as triethylamine or dimethylbenzylamine as a catalyst. In this case, the total of the hydroxyl group-containing urethane prepolymer (c) and the acid anhydride group-containing compound (d). It is preferable to add 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 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g. When the acid value is less than 10 mg KOH / g, sufficient developability may be difficult to obtain. For example, the film may remain as a residue in a portion where the film is dissolved and removed during development. Moreover, when an acid value exceeds 200 mgKOH / g, the solubility of the coating film with respect to a developing solution becomes high, and even the part which wants to make it photocure and leave as a pattern melt | dissolves, and the shape of a pattern may deteriorate.

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, and more preferably 300 to 2000 g / eq. When the ethylenically unsaturated group equivalent is less than 200 g / eq, the photosensitivity may be too high, and even the part to be removed by dissolving the film during development is cured by light, and a good pattern shape is obtained. There may not be. When the ethylenically unsaturated group equivalent exceeds 3000 g / eq, the photosensitivity may be too low, the portion to be photocured may not be sufficiently cured, and the pattern dissolves during development, thereby obtaining a good pattern shape. There may not be.
The “ethylenically unsaturated group equivalent” as used in the present invention is a theoretical value calculated from the weight of raw materials used during the synthesis of the resin, and the weight of the resin is the ethylenically unsaturated group present in the resin. It is divided by the number of groups and corresponds to the weight of the resin per mole of ethylenically unsaturated groups, 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 1000 to 100,000, more preferably 3000 to 60000. If the weight average molecular weight is less than 1000, sufficient solder heat resistance and flexibility may not be obtained. On the other hand, when the weight average molecular weight exceeds 100,000, the soldering heat resistance is excellent, but the developability may be deteriorated, and the viscosity and handling at the time of coating may be problems.

The production method of the carboxyl group-containing photosensitive urethane resin (A) according to the present invention comprises a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g). A first step of reacting as a component to obtain a carboxyl group-containing urethane prepolymer (a);
The hydroxyl group-containing urethane prepolymer (c) obtained by reacting the carboxyl group-containing urethane prepolymer (a) obtained in the first step with the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group. A second step of obtaining
Furthermore, a third step of reacting the hydroxyl group-containing urethane prepolymer (c) obtained in the second step with the acid anhydride group-containing compound (d) is included.

  As reaction conditions of the first step, it is preferable to carry out the reaction by heating and stirring at a temperature of room temperature or higher and 180 ° C. or lower, and a reaction catalyst can be used as necessary. As the reaction conditions for the second step, it is preferable to react by heating and stirring at a temperature of 50 to 150 ° C. in the presence of oxygen. If necessary, a reaction catalyst and a polymerization inhibitor of an ethylenically unsaturated group are added. It can also be used. Moreover, as the reaction conditions of the third step, it is preferable to carry out the reaction by heating and stirring at 50 to 150 ° C. in the presence of oxygen, as in the second step. It is also possible to newly add a suitable reaction catalyst and a polymerization inhibitor for ethylenically unsaturated groups.

  Moreover, when manufacturing a carboxyl group-containing urethane prepolymer (a) in a 1st process, a polymer polyol (e), the carboxylic acid compound (f) which has two hydroxyl groups in a molecule | numerator, and a diisocyanate compound (g). As an essential component, and further, reacting the hydroxyl group-containing compound (h) as an optional component, the isocyanate compound (i) as an optional component, and the amine compound (j) as an optional component. it can.

  Moreover, the solvent used for the synthesis | combination of the said carboxyl group-containing photosensitive urethane resin (A) can be suitably selected according to the end use and the solubility of a reaction material. For example, when a dry film type photosensitive solder resist is used as the final application, it is preferable to use a low-boiling solvent because the solvent needs to be quickly dried in the dry film preparation step. Examples of the low boiling point solvent in this case include methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol and the like. In addition, when liquid solder resist ink is used as the final application, it is necessary to suppress volatilization of the solvent as much as possible in consideration of the process of kneading fillers and pigments with rolls in the ink preparation process and the storage stability as ink. Therefore, it is preferable to use a high boiling point solvent. Examples of the high boiling point solvent in this case include carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone and the like.

  In the present invention, these solvents may be used alone or in combination, if necessary, and may be used in combination. Or a solvent may be added.

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

  The photopolymerization initiator (B) is added for the purpose of curing the photosensitive compound with active energy rays (for example, ultraviolet rays). The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl A compound etc. can be used.

  Specific examples of monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-enetanone. 3,3′-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3′4,4′-tetra ( t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-n- [2 (1-Oxo-2-propenyloxyethyl)] metaammonium bromide, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1, 2-d) thiazoline and the like.

  Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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 polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla No-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2- Morpholino-propanonyl) -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 normal butyl ether.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide, and the like.

  Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis- (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.

  In particular, in the present invention, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and thioxanthones are used in combination, the photosensitivity is very low, though it is inexpensive. It is particularly preferred because of its superiority.

These are not limited to the above compounds, and any compounds may be used as long as they have the ability to initiate polymerization by active energy rays. These can be used alone or in combination, and the amount used is not limited, but is added in the range of 1 to 20 parts by weight with respect to 100 parts by weight as the total dry weight of the carboxyl group-containing photosensitive urethane resin (A). It is preferable. Moreover, a well-known organic amine can also 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 a general photosensitive compound usually blended in a photosensitive solder resist ink or the like, and has an ethylenically unsaturated double bond in the structure. In the present invention, among these general photosensitive compounds, photosensitive compounds not included in the definition of the “carboxyl group-containing urethane resin (A)” are photosensitive ethylenically unsaturated group-containing compounds (C). Can be used as The photosensitive ethylenically unsaturated group-containing compound (C) that can be used in the present invention has an ethylenically unsaturated double bond in the structure, and the above-mentioned “carboxyl group-containing urethane resin (A)”. As long as it is not included in the specification, it is not particularly limited. For example, an alkyl (meth) acrylate, an alkylene glycol (meth) acrylate, a compound having a carboxyl group and an ethylenically unsaturated group [however, the carboxyl group Excluding compounds included in the definition of the containing urethane resin (A)], (meth) acrylate compounds having a hydroxyl group, nitrogen-containing (meth) acrylate compounds, and the like. Moreover, a monofunctional and polyfunctional compound can be used suitably. From the viewpoint of photocurability and hard coat properties of the coating film, polyfunctional ones are preferred.

  More specifically, as the alkyl-based (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) Acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadeci When there is an alkyl (meth) acrylate having an alkyl group having 1 to 22 carbon atoms such as (meth) acrylate, icosyl (meth) acrylate, heicosyl (meth) acrylate, docosyl (meth) acrylate, etc. Preferably, an alkyl (meth) acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms is used.

Examples of the alkylene glycol (meth) acrylate include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, hexaethylene glycol mono (meth) acrylate, and 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 a polyoxyalkylene chain;
Methoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, propoxytetraethylene glycol (meth) acrylate , N-butoxytetraethylene glycol (meth) acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy Tetrapropylene glycol (meth) acrylate, ethoxytetrapropyleneglycol (Meth) acrylate, propoxytetrapropylene glycol (meth) acrylate, n-butoxytetrapropylene glycol (meth) acrylate, n-pentoxytetrapropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetra Methylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, mono (meth) acrylate having an alkoxy group at the terminal and a polyoxyalkylene chain;
Phenoxydiethylene glycol (meth) acrylate, phenoxyethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, Examples thereof include polyoxyalkylene (meth) acrylates having a phenoxy group or an aryloxy group at the terminal, such as phenoxytetrapropylene glycol (meth) acrylate.

  Examples of the compound having a carboxyl group and an ethylenically unsaturated group excluding the carboxyl group-containing urethane resin (A) include maleic acid, fumaric acid, itaconic acid, citraconic acid, or alkyl or alkenyl monoesters thereof, phthalates Acid β- (meth) acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth) acryloxyethyl monoester And acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and the like.

  Moreover, as a compound which has a hydroxyl group and an ethylenically unsaturated group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene and the like are listed.

Examples of the compound having a nitrogen atom and an ethylenically unsaturated group include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl- (meth) acrylamide, N-ethoxymethyl- (meth) acrylamide, Monoalkylol (meth) acrylamides such as N-propoxymethyl- (meth) acrylamide, N-butoxymethyl- (meth) acrylamide, N-pentoxymethyl- (meth) acrylamide, N, N-di (methylol) acrylamide, N-methylol-N-methoxymethyl (meth) acrylamide, N, N-di (methoxymethyl) acrylamide, N-ethoxymethyl-N-methoxymethylmethacrylamide, N, N-di (ethoxymethyl) acrylamide, N-ethoxy Methyl-N-propoxy Methylmethacrylamide, N, N-di (propoxymethyl) acrylamide, N-butoxymethyl-N- (propoxymethyl) methacrylamide, N, N-di (butoxymethyl) acrylamide, N-butoxymethyl-N- (methoxymethyl) ) Acrylamide unsaturated compounds such as dialkyl (meth) acrylamides such as methacrylamide, N, N-di (pentoxymethyl) acrylamide, N-methoxymethyl-N- (pentoxymethyl) methacrylamide, dimethylaminoethyl (meta ) Unsaturated compounds having a dialkylamino group such as acrylate, diethylaminoethyl (meth) acrylate, methylethylaminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene, and the counter ion l ^{-, Br -,} I ^- halogen ions, such as, or ^QSO 3-: having (Q alkyl group having 1 to 12 carbon atoms) can be exemplified by quaternary ammonium salts of dialkylamino group-containing unsaturated compound.

Further, other unsaturated compounds include perfluoromethylmethyl (meth) acrylate, perfluoroethylmethyl (meth) acrylate, 2-perfluorobutylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2 -Perfluorooctylethyl (meth) acrylate, 2-perfluoroisononylethyl (meth) acrylate, 2-perfluorononylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, perfluoropropylpropyl (meth) ) Acrylate, perfluorooctylpropyl (meth) acrylate, perfluorooctyl amyl (meth) acrylate, perfluorooctyl undecyl (meth) acrylate, etc. Perfluoroalkyl (meth) acrylates having Kill group;
Perfluoroalkyl group-containing vinyl monomers such as perfluoroalkyl, alkylenes such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene, perfluorodecylethylene;
Alkoxysilyl group-containing vinyl compounds such as vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane and derivatives thereof;
Examples thereof include glycidyl group-containing (meth) acrylates such as glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate, and one or more types can be appropriately selected from these groups and used.

Moreover, as a fatty acid vinyl compound, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl hexanoate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, etc .;
Examples of alkyl vinyl ether compounds include butyl vinyl ether and ethyl vinyl ether;
As the α-olefin compound, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and the like;
As vinyl compounds, allyl compounds such as allyl acetate, allyl alcohol, allylbenzene, allyl cyanide, vinyl cyanide, vinylcyclohexane, vinyl methyl ketone, styrene, α-methylstyrene, 2-methylstyrene, chlorostyrene, etc .;
As an ethynyl compound, acetylene, ethynylbenzene, ethynyltoluene, 1-ethynyl-1-cyclohexanol and the like;
Can also be used.

  Next, a polyfunctional compound having two or more ethylenically unsaturated groups is specifically exemplified.

  First, an aliphatic compound is illustrated among the compounds which have an ethylenically unsaturated group. Specifically, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Bis (acryloxy neopentyl glycol) adipate, bis (methacryloxy neopentyl glycol) adipate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate: Nippon Kayaku Kayrad R-167, hydroxypivalate neopentyl glycol di (Meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate: Nippon Kayaku Kayrad HX series alkyl type (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, epichlorohydrin modified ethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -811, epichlorohydrin modified diethylene glycol di (meth) acrylate: Nagase Sangyo Denacol DA (M) -851, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene Recall di (meth) acrylate: alkylene glycol type (meth) acrylate such as Nagase Sangyo Denacol DA (M) -911, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, neopentyl glycol modified trimethylolpropane Di (meth) acrylate: Nippon Kayaku Kayrad R-604, ethylene oxide modified trimethylolpropane tri (meth) acrylate: Sartomer SR-454, propylene oxide modified trimethylolpropane tri (meth) acrylate: Nippon Kayaku TPA- 310, trichlorohydrin-modified trimethylolpropane tri (meth) acrylate: trimethylolpropane type (meth) acrylate such as Nagase Sangyo DA (M) -321, penta Erythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate: Toa Synthetic Aronix M-233, dipentaerythritol hexa (meth) acrylate, dipentaerythritol monohydroxypenta (meta ) Acrylate, alkyl-modified dipentaerythritol poly (meth) acrylates: Kayarad D-310, 320, 330 made by Nippon Kayaku, etc. Caprolactone-modified dipentaerythritol poly (meth) acrylates: Kayrad DPCA-20 made by Nippon Kayaku Pentaerythritol type (meth) acrylate such as 30, 60, 120, glycerol di (meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate Rate: Nagase Sangyo Denacol DA (M) -314, glycerol type (meth) acrylate such as triglycerol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, tricyclopentanyl di (meth) acrylate, cyclohexyldi (Meth) acrylate, methoxylated cyclohexyl di (meth) acrylate: cycloaliphatic (meth) acrylate such as Sanyo Kokusaku Pulp CAM-200, tris (acryloxyethyl) isocyanurate: Toa Gosei Aronix M-315, Tris (methacryloxy) Isocyanurate type (meth) acrylates such as ethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, caprolactone-modified tris (methacryloxyethyl) isocyanurate, etc. It is below.

  Of the compounds having an ethylenically unsaturated group, aromatic compounds are exemplified. For example, hydroquinone, resorcin, catechol, pyrogallol, bisphenol A di (meth) acrylate, ethi (propyrene) oxide-modified bisphenol A di (meth) acrylate [“ethi (propyrene) oxide” means “ethylene oxide” or “propylene” Means "oxide". The same applies below. ], Bisphenol F di (meth) acrylate, Ethi (propi) ylene oxide modified bisphenol F di (meth) acrylate, Bisphenol S di (meth) acrylate, Ethi (propi) lene oxide modified bisphenol S di (meth) acrylate, Epichlorohydrin modified (Meth) acrylate compounds having aromatic groups such as di (meth) acrylate phthalate, tetrachlorobisphenol S ethyl (propylene) oxide modified di (meth) acrylate, tetrabromobisphenol S ethyl (propylene) oxide modified di (meth) Examples thereof include styrenes having an aromatic group substituted with a halogen atom having an atomic weight of not less than a chlorine atom, such as acrylate, and (meth) acrylate compounds.

  Furthermore, polyfunctional (meth) acrylates such as urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate are preferably used as the compound (C) from the viewpoint of coating film strength and scratch resistance. be able to. Epoxy (meth) acrylate is obtained by esterifying an epoxy group of an epoxy resin with (meth) acrylic acid and converting the functional group to (meth) acrylate, and (meth) acrylic acid adduct to bisphenol A type epoxy resin. And (meth) acrylic acid adducts to novolac epoxy resins. Urethane (meth) acrylates are, for example, those obtained by reacting diisocyanates with (meth) acrylates having a hydroxyl group, and isocyanate group-containing urethane prepolymers obtained by reacting polyols and polyisocyanates under conditions of excess isocyanate groups. Some are obtained by reacting polymers with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under hydroxyl-excess conditions can be obtained by reacting with a (meth) acrylate having an isocyanate group.

The following can be illustrated as a commercial item.
Toa Gosei 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 Chemical Industry Co., Ltd .: Biscote # 400;
Kayaku Sartomer Co., Ltd .: SR-295;
Made by Daicel UCB Corporation: DPHA, Ebecryl 220, Ebecryl 1290K, Ebecryl 5129, Ebecryl 2220, Ebecryl 6602;
Shin-Nakamura Chemical Co., Ltd .: NK Ester A-TMMT, NK Oligo EA-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: LaromerEA81;
San Nopco Co., Ltd .: Photomer 3016;
Arakawa Chemical Industries, Ltd .: beam set 371, beam set 575, beam set 577, beam set 700, beam set 710;
Manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin HDP, Art Resin HDP- 3, Art Resin H61;
Nippon Synthetic Chemical Industry Co., Ltd .: Purple light UV-7600B, Purple light UV-7610B, Purple light UV-7620EA, Purple light UV-7630B, Purple light UV-1400B, Purple light UV-1700B, Purple light UV-6300B;
Kyoeisha Chemical Co., Ltd .: Light acrylate PE-4A, Light acrylate DPE-6A, UA-306H, UA-306T, UA-306I;
Nippon Kayaku Co., Ltd .: KAYARAD DPHA, KAYARAD DPHA2C, KAYARAD DPHA-40H, KAYARAD D-310, KAYARAD D-330, SR-35;
Etc.

  As described above, the photosensitive ethylenically unsaturated group-containing compound (C) is usually blended in a photosensitive solder resist ink or the like. For example, the carboxyl group-containing compound improves the developability and thermosetting of the composition. It is known that a hydroxyl group-containing compound improves the adhesion and developability of the composition to a substrate. Accordingly, also in the present invention, as the photosensitive ethylenically unsaturated group-containing compound (C), a carboxyl group-containing compound (however, excluding a compound included in the definition of the carboxyl group-containing urethane resin (A)) is a composition. It is preferable to use it when improving the developability and thermosetting property, and it is preferable to use the hydroxyl group-containing compound when improving the adhesion and developability of the composition to the substrate. In addition, a polyfunctional compound having two or more ethylenically unsaturated groups can be used for improving the photosensitivity and resolution of the composition, and the aromatic unsaturated compound is used for the heat resistance of the coating film. It is preferable to use it for improving the refractive index and controlling the refractive index. Furthermore, oligomer type (meth) acrylates such as urethane (meth) acrylate and epoxy (meth) acrylate are preferably used for the purpose of improving the strength and scratch resistance of the coating film.

  Further, those containing an ethylene oxide addition structure in the molecule and glycol-modified (meth) acrylates (for example, Aronix M-310 manufactured by Toagosei Co., Ltd. and SR-355 manufactured by Nippon Kayaku Co., Ltd.) have high hydrophilicity. Further, since the viscosity is further low, the use of these compounds in the present invention is particularly preferable because a photosensitive resin composition having very excellent developability and resolution can be obtained.

  The photosensitive ethylenically unsaturated group-containing compound (C) is preferably used in an amount of 0.1 to 300 parts by weight with respect to 100 parts by weight of the carboxyl group-containing photosensitive urethane resin (A). It is more preferable to use 200 parts by weight, and it is even more preferable to use 5 to 100 parts by weight. The photosensitive ethylenically unsaturated group-containing compound (C) is used for the purpose of adjusting the photosensitivity and resolution of the photosensitive resin composition. If the amount is less than 0.1 part by weight, the photosensitivity of the photosensitive resin composition may be insufficient. If the amount exceeds 300 parts by weight, there may be a problem in flexibility.

  In addition to the carboxyl group-containing photosensitive urethane resin (A), the photopolymerization initiator (B), and the photosensitive ethylenically unsaturated compound (C), the photosensitive resin composition of the present invention is further thermoset. It is preferable that a thermosetting compound (D) is included, and it is still more preferable that a thermosetting compound (D) and a thermosetting adjuvant (E) are included.

  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 capable of reacting with the functional group contained in the carboxyl group-containing photosensitive urethane resin (A). In the present invention, the functional group that reacts 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 capable of reacting with a hydroxyl group include polyisocyanate compounds, amino resins, phenol resins, and polyfunctional polycarboxylic acid anhydrides.

  The polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanate groups in the molecule. Examples of polyisocyanate compounds include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane trisene. Polyisocyanate compounds such as isocyanate and polymethylene polyphenyl isocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, burettes and isocyanurates of these polyisocyanate compounds, and further these polyisocyanate compounds Known polyether polyols and polyesters Ether polyols, acrylic polyols, polybutadiene polyols, adducts, etc. and polyisoprene polyol and the like.

  Examples of amino resins and phenol resins include addition compounds of compounds such as urea, melamine, benzoguanamine, phenol, cresols, bisphenols and formaldehyde, or partial condensates thereof.

  The polyfunctional polycarboxylic acid anhydride is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride And polyvalent carboxylic acid anhydrides such as maleic anhydride copolymer resins. In addition, polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that can be converted into an anhydride via a dehydration reaction during the reaction are “compounds having two or more carboxylic acid anhydride groups” in the present invention. "include.

  More specifically, as tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenyl sulfone tetracarboxylic dianhydride, Diphenyl sulfide tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, perylene tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, "Ricacid TMTA-C", "Ricacid MTA-" manufactured by Shin Nippon Chemical Co., Ltd. 10 ”,“ Licacid MTA-15 ”,“ Licacid TMEG series ”,“ Licacid TDA ”, and the like.

  Examples of maleic anhydride copolymer resins include SMA resin series manufactured by Sartomer, GSM series manufactured by Gifu Shellac Co., Ltd., styrene-maleic anhydride copolymer resins, p-phenylstyrene-maleic anhydride copolymer resins, polyethylene- Α-olefin-maleic anhydride copolymer resins such as maleic anhydride, “VEMA” (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., and acrylic anhydride-modified polyolefin (“aurolen series”) ": Nippon Paper Chemical Co., Ltd.), maleic anhydride copolymer acrylic resin, and the like.

  Examples of the thermosetting component (D) having at least two functional groups capable of reacting with a carboxyl group include compounds (k) having two or more epoxy groups or oxetane groups, polyfunctional vinyl ether compounds, high molecular weight polycarbodiimides, Examples include aziridine compounds. Among these, the compound (k) having two or more epoxy groups or oxetane groups is very preferable in terms of the curing speed and the durability of the cured product.

  The compound (k) having two or more epoxy groups or oxetane groups may be a compound having two or more epoxy groups or oxetane groups in the molecule, and is not particularly limited. Specific examples of the compound having an epoxy group as the compound (k) include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A / epichlorohydrin type epoxy. Resin, bisphenol F / epichlorohydrin type epoxy resin, biphenol / epichlorohydrin type epoxy resin, polyglycidyl ether of glycerin / epichlorohydrin adduct, phenol novolac type epoxy resin, cresol novolac type epoxy resin, JP2001-240654A Dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, polyglycidyl ether of ethylene glycol / epichlorohydrin adduct, Intererythritol polyglycidyl ether, resorcinol diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexahydrophthalic acid diglycidyl ester Hydrogenated bisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N-diglycidyl aniline, N, N-diglycidyl toluidine, JP-A No. 2004-156024, JP-A No. 2004-31559 JP-epoxy compound and having excellent flexibility as disclosed in JP-A-2004-323777, epoxy compounds having a structure represented by the following formula (1) to (3), and the like.

Formula (1)

Formula (2)

Formula (3)

  As the compound having an oxetane group as the compound (k), specifically, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, (2-ethyl-2-oxetanyl) ) Esterified product of ethanol and terephthalic acid, etherified product of (2-ethyl-2-oxetanyl) ethanol and phenol novolac resin, esterified product of (2-ethyl-2-oxetanyl) ethanol and polyvalent carboxylic acid compound, etc. Is mentioned.

  As the compound (k), in particular, an aliphatic epoxy compound or an epoxy compound described in JP-A No. 2004-156024, JP-A No. 2004-315595, or JP-A No. 2004-323777 can be used as a cured coating film. It is preferable because of its excellent flexibility. Further, dicyclopentadiene type epoxy compounds described in JP-A-2001-240654, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenol / epichlorohydrin type epoxy resins, 4,4′-bis [(3 -Ethyl-3-oxetanyl) methoxymethyl] biphenyl, esterified product of (2-ethyl-2-oxetanyl) ethanol and terephthalic acid, etc. in the present invention are cured including thermosetting, hygroscopicity and heat resistance. It is excellent in terms of durability of the coating film and is preferable.

  Specific examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and 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-dihydroxylcyclohexane divinyl ether, 1,4 -Dihydroxymethylcyclohexanedivinyl ether, Hyde Quinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcin divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerin trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol Examples include trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, and ditrimethylolpropane polyvinyl ether.

  Examples of the high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.

  Examples of the aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.

  Other thermosetting compounds (D) include benzoxazine compounds, benzocyclobutene compounds, maleimide compounds, nadiimide compounds, allyl nadiimide compounds, melamine compounds, guanamine compounds, blocked isocyanate compounds, etc. Any of these can be used effectively. These photopolymerizable groups, functional groups capable of reacting with carboxyl groups, and compounds having functional groups capable of reacting with hydroxyl groups can improve the heat resistance of the coating film after curing, and are therefore used more effectively. be able to.

  These thermosetting compounds (D) may use only 1 type and may use 2 or more types together. The amount of the thermosetting compound (D) used may be determined in consideration of the use of the photosensitive resin composition and the like, and is not particularly limited. However, the carboxyl group-containing photosensitive urethane resin (A) is 100 weights. Is more preferably in the range of 0.1 to 100 parts by weight, and still more preferably in the range of 0.5 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 usage-amount of a thermosetting compound (D) is less than 0.1 weight part, the crosslinking density of the coating film after heat-curing will become low too much, and cohesion force and durability may become inadequate. In addition, when the amount used is more than 100 parts by weight, the crosslinking density after heat curing becomes too high, resulting in a decrease in the flexibility and flexibility of the coating film, and the deterioration of the substrate warpage. There is.

  Next, the thermosetting aid (E) will be described. The term “thermosetting aid” as used herein refers to a compound that contributes directly or catalytically to the curing reaction during thermosetting.

  The thermosetting aid (E) is appropriately selected depending on the thermosetting compound (D) used. Moreover, the curing conditions for the carboxyl group-containing photosensitive urethane resin (A) and the thermosetting compound (D) can be appropriately selected depending on the thermosetting compound (D) and the thermosetting aid (E) used.

Examples of the heat curing aid (E) include tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine, and salts thereof;
2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl-1] -Imidazoles such as ethyl-S-triazine and salts thereof;
1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diabicyclo [2,2,2,] octane, etc. Diazabicyclo compounds;
Phosphines such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine;
Phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate;
In addition, dicyandiamide, carboxylic acid hydrazide, and the like can be cited as compounds that are catalytic and that directly contribute to the curing reaction. Examples of the carboxylic acid hydrazide include succinic acid hydrazide and adipic acid hydrazide.

  In the present invention, when an epoxy compound is used as the thermosetting compound (D), the use of dicyandiamide, carboxylic acid hydrazide, imidazoles, or diazabicyclo compounds as the thermosetting aid (E) is more efficient. It is preferable because the curing reaction proceeds and the coating film has excellent resistance.

  Moreover, in this invention, it is preferable to use a thermosetting adjuvant (E) in the range of 0.1-10 weight part with respect to 100 weight part of carboxyl group-containing photosensitive urethane resin (A), 0 More preferably within the range of 5 to 8 parts by weight. If the amount used is less than 0.1 parts by weight, sufficient effects as a thermosetting aid cannot be exhibited, and eventually the cohesive strength and durability of the coating film may be insufficient. On the other hand, when the amount used is more than 10 parts by weight, an excessive thermosetting auxiliary agent may remain in the system, which may deteriorate various physical properties of the coating film such as bleeding and deterioration of insulation properties.

  The photosensitive resin composition of this invention may contain resin other than said carboxyl group-containing photosensitive urethane resin (A) and the photosensitive ethylenically unsaturated group containing compound (C) as needed. Resins other than the carboxyl group-containing photosensitive urethane resin (A) and the photosensitive ethylenically unsaturated group-containing compound (C) include acrylic resins, polyester resins, urethane resins, urea resins, urethane urea resins, epoxy resins, polyamide resins. And polyimide resin. From the viewpoint of developability, these preferably contain a carboxyl group, and are compatible with the carboxyl group-containing photosensitive urethane resin (A) and the photosensitive ethylenically unsaturated group-containing compound (C). A superior one is preferred. In the present invention, when a resin other than the carboxyl group-containing photosensitive urethane resin (A) and the photosensitive ethylenically unsaturated group-containing compound (C) is contained, it can be used alone or in combination.

  In addition to the above, the photosensitive resin composition of the present invention may further include solvents, dyes, pigments, flame retardants, antioxidants, polymerization inhibitors, leveling agents, humectants, viscosity modifiers as optional components within a range not to impair the purpose. Preservatives, antibacterial agents, antistatic agents, anti-blocking agents, ultraviolet absorbers, infrared absorbers, electromagnetic shielding agents, fillers, and the like can be added. Especially used for insulating materials (such as circuit protection films, coverlay layers, interlayer insulating materials, etc.) that are in direct contact with the circuit for electronic materials, and for members that can become high heat around the circuit (printed wiring board adhesive, support substrate, etc.) When doing so, it is preferable to use a flame retardant together.

  Examples of the flame retardant include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium polyphosphate, carbamate phosphate, and carbamate polyphosphate. Phosphate compounds and polyphosphate compounds, red phosphorus, organophosphate compounds, phosphazene compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, phosphoramide compounds and other phosphorus flame retardants, melamine, Triazine compounds such as melam, melem, melon, melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, nitrogen flame retardants such as urea, Silicon flame retardants such as corn compounds and silane compounds, low molecular halogen-containing compounds such as halogenated bisphenol A, halogenated epoxy compounds and halogenated phenoxy compounds, halogen flame retardants such as halogenated oligomers and polymers, hydroxylation Metal hydroxide such as aluminum, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate Inorganic flame retardants such as magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and hydrated glass. In the present invention, taking into consideration the influence on the environment, which has been recently taken into consideration, it is desirable to use a non-halogen flame retardant such as a phosphorus flame retardant or a nitrogen flame retardant, and among others, the photosensitive resin composition of the present invention. It is preferable to use a phosphazene compound, a phosphine compound, melamine polyphosphate, ammonium polyphosphate, melamine cyanurate, etc., which are more effective in flame retardancy. In the present invention, these flame retardants can be used alone or in combination.

  Since the photosensitive resin composition of the present invention and its cured product are characterized by excellent alkali developability, they can be suitably used for applications in which a film forming process including photocuring, alkali development, and post-cure is used. . Furthermore, since it is excellent in solder heat resistance and coating film resistance, and is also excellent in flexibility and flexibility, it is particularly suitable for use in solder resist inks for flexible printed wiring boards and photosensitive coverlay films. it can.

  The photosensitive resin composition of the present invention can be applied to a metal, ceramics, glass, plastic, wood, slate or the like as a substrate, and is not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Moreover, as a shape of a base material, although a film sheet, a plate-shaped panel, a lens shape, a disk shape, and a fiber-like thing are mentioned, it does not restrict | limit in particular.

The photosensitive resin composition of the present invention can be cured by a known radiation curing method to obtain a cured product, and as active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. 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 as a source (light source) for ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated, can be set appropriately in the range of 5~2000mJ / cm ^2, it is preferably in the range on the easy of 50~1000mJ / cm ² management process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high frequency heating or the like.

  When used as a photo solder resist, the photosensitive resin composition of the present invention can be used as a liquid resist ink dissolved in a solvent or a dry film type resist obtained by previously drying the solvent.

  When used as a liquid resist ink, the photosensitive resin composition of the present invention may be subjected to radiation curing after the solvent is volatilized by natural or forced drying after coating on the substrate, and subsequent to coating. Although natural or forced drying may be performed after the radiation curing, it is preferable that the radiation curing is performed after natural or forced drying. In the case of liquid resist ink, it is preferable that the solvent does not evaporate during handling until the application to the substrate is completed, such as the storage step and the coating step. As the dilution solvent at the time of ink preparation, those having a high boiling point are preferable. For example, it is particularly preferable to use carbitol acetate, methoxypropyl acetate, cyclohexanone, diisobutyl ketone or the like. In addition, in the case of liquid resist inks, there are also two-component types that are stored in advance separately from the curing agent in consideration of storage stability and handling, and mixed with a curing agent as necessary before coating. is there. Also in the case of the present invention, the photopolymerization initiator (B), the thermosetting compound (D), and the thermosetting auxiliary agent (E) are stored separately from the others as necessary. It can also be used as a liquid form.

  On the other hand, when used as a dry film type resist, a dry film type is obtained by first applying a photosensitive composition dissolved in a solvent to a film substrate having good releasability such as a separate film and then drying the solvent. Create a resist. In this case, unlike the above-described liquid resist ink, it is necessary to dry the solvent completely in a short time, and therefore a solvent having a low boiling point is preferable. For example, it is particularly preferable to use methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran, toluene, isopropyl alcohol, or the like. The dry film formed on the separate film is laminated on a copper circuit or the like formed on polyimide, and thereafter, bubbles and the like are removed and adhered to the circuit by lamination or vacuum lamination. After this pasting step, there may be a case where the radiation curing is performed through a separate film, or a case where the development pattern is brought into contact after the separation film is peeled to perform the radiation curing. When radiation curing is performed by bringing a development pattern into contact, if the dry film has a tack, the development pattern may be contaminated. Therefore, a dry film type resist is required to have a low dry film tack. Since the photosensitive resin composition of this invention can reduce a tack as needed, it can be usefully used also as a dry film resist.

  Furthermore, the photosensitive resin composition of the present invention forms a pattern by developing after radiation curing, and forms a film having excellent resistance by thermosetting as post-cure. The post cure is preferably 30 to 2 hours at 100 to 200 ° C. Moreover, in order to improve the tolerance of a coating film, an active energy ray can be irradiated as needed even after the post cure. By irradiating the active energy ray after the post cure, the solder heat resistance and the like can be further improved.

  The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

  The measurement conditions for GPC are as follows.

<Measurement of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. For the measurement in the present invention, “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) is connected in series to the column, the flow rate is 0.6 ml / min, the column temperature. It carried out on the conditions of 40 degreeC, and the determination of the weight average molecular weight (Mw) was performed in polystyrene conversion.

[Production Example 1]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 13,000 and an actually measured resin solid acid value of 98 mgKOH / g.

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

  Next, 63 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 863 g / eq, the weight average molecular weight in terms of polystyrene is 15400, and the acid value of the resin solid content by actual measurement is It was 73 mgKOH / g.

[Production Example 2]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 4 parts of polytetramethylene glycol (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) In addition, 201 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring under a nitrogen stream and dissolved uniformly. Subsequently, 296 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 8900 and an actually measured resin solid acid value of 152 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 193 parts of glycidyl methacrylate, 7 parts of dimethylbenzylamine and 0.4 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 9600 and an actually measured resin solid acid value of 1 mgKOH / g.

  Next, 136 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 611 g / eq, the weight average molecular weight in terms of polystyrene is 11020, and the acid value of the resin solid content measured is It was 92 mgKOH / g.

[Production Example 3]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 318 parts of polytetramethylene glycol (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 46 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen stream to dissolve the mixture uniformly. Subsequently, 136 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 19,800 and an actually measured resin solid acid value of 35 mgKOH / g.

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

  Next, 31 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 1846 g / eq, the polystyrene-equivalent weight average molecular weight is 23100, and the acid value of the resin solid content measured is It was 30 mgKOH / g.

[Production Example 4]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 140 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) In addition, 115 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen stream to dissolve the mixture uniformly. Subsequently, 244 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-reduced weight average molecular weight of 48900 and an actually measured acid value of 87 mgKOH / g of resin solids.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-reduced weight average molecular weight of 52,200 and an actually measured acid value of resin solids of 5 mgKOH / g.

  Next, 78 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared according to this production example is 884 g / eq, the weight average molecular weight in terms of polystyrene is 54000, and the acid value of the resin solid content by actual measurement is It was 68 mgKOH / g.

[Production Example 5]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet pipe, an inlet pipe, and a thermometer, 164 parts of polytetramethylene glycol (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) In addition, 135 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring under a nitrogen stream and dissolved uniformly. Subsequently, 202 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-reduced weight average molecular weight of 3900 and an actually measured acid value of 102 mgKOH / g of resin solids.

  Next, nitrogen from the nitrogen inlet tube was stopped in this flask, switching to introduction of dry air, 103 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-reduced weight average molecular weight of 4600 and an actually measured resin solid acid value of 17 mgKOH / g.

  Next, 65 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 920 g / eq, the weight average molecular weight in terms of polystyrene is 5100, and the acid value of the resin solid content by actual measurement is It was 71 mg KOH / g.

[Production Example 6]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 13,000 and an actually measured resin solid acid value of 98 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 156 parts of 4-hydroxybutyl acrylate glycidyl ether (Nihon Kasei Co., Ltd .: 4-HBAGE) with stirring, dimethylbenzylamine 7 parts and further 0.3 parts of hydroquinone as a polymerization inhibitor were added and reacted at 90 ° C. for 8 hours. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 16,500 and an actually measured resin solid acid value of 9 mgKOH / g.

  Next, 70 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 931 g / eq, the weight average molecular weight in terms of polystyrene is 18800, and the acid value of the resin solid content by actual measurement is It was 65 mgKOH / g.

[Production Example 7]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer, 156 parts of polytetramethylene glycol (PTG1000sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g), dimethylolbutane 129 parts of acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen stream to dissolve the mixture uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 13,000 and an actually measured resin solid acid value of 98 mgKOH / g.

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

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

[Production Example 8]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 13,000 and an actually measured resin solid acid value of 98 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 55 parts of glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether (Nihon Kasei Co., Ltd .: 4-HBAGE) 78 with stirring. Part, 7 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added and reacted at 90 ° C. for 8 hours. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-reduced weight average molecular weight of 16900 and an actually measured resin solid acid value of 7 mgKOH / g.

  Next, 72 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 885 g / eq, the weight average molecular weight in terms of polystyrene is 17300, and the acid value of the resin solid content by actual measurement is It was 68 mgKOH / g.

[Production Example 9]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 13,000 and an actually measured resin solid acid value of 98 mgKOH / g.

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

  Next, 53 parts of tetrahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd .: Ricacid TH) and 35 parts of succinic anhydride were added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 840 g / eq, the weight average molecular weight in terms of polystyrene is 17100, and the acid value of the resin solid content by actual measurement is It was 72 mgKOH / g.

[Production Example 10]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) In addition, 128 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen stream to dissolve the mixture uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-reduced weight average molecular weight of 14100 and an actually measured resin solid acid value of 97 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 133 parts of oxetanyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. , Reacted at 95 ° C. for 16 hours. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 15100 and an actually measured resin solid acid value of 7 mgKOH / g.

  Next, 70 parts of succinic anhydride was added to the flask and allowed to react for 6 hours while stirring at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 901 g / eq, the weight average molecular weight in terms of polystyrene is 16300, and the acid value of the resin solid content by actual measurement is It was 69 mgKOH / g.

[Production Example 11]
Polycarbonate diol (Kuraray polyol C-1090: manufactured by Kuraray Co., Ltd .: hydroxyl value = 112 mgKOH / g, Mw = 1002) 156 is added to a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer. Part, dimethylol butanoic acid (manufactured by Nippon Kasei Co., Ltd.) 129 parts and cyclohexanone 375 parts as a solvent were charged and heated up to 60 ° C. with stirring in a nitrogen stream to be uniformly dissolved. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 23100 and an actually measured resin solid acid value of 100 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 24600 and an actually measured resin solid acid value of 7 mgKOH / g.

  Next, 63 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 870 g / eq, the polystyrene-equivalent weight average molecular weight is 25500, and the acid value of the resin solid content by actual measurement is It was 70 mgKOH / g.

[Production Example 12]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) In addition, 129 parts of dimethylolpropionic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the temperature was raised to 60 ° C. with stirring in a nitrogen stream to dissolve it uniformly. Subsequently, 215 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After the reaction was completed, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 18700 and an actually measured acid value of 102 mgKOH / g.

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

  Next, 63 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 851 g / eq, the weight average molecular weight in terms of polystyrene is 22600, and the acid value of the resin solid content by actual measurement is It was 74 mgKOH / g.

[Production Example 13]
In a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 156 parts of polytetramethylene glycol (PTG1000 sn: manufactured by Hodogaya Chemical Co., Ltd .: hydroxyl value = 110 mgKOH / g, Mw = 1020) Then, 129 parts of dimethylolbutanoic acid (manufactured by Nippon Kasei Co., Ltd.) and 375 parts of cyclohexanone as a solvent were charged, and the mixture was heated to 60 ° C. with stirring in a nitrogen stream, and dissolved uniformly. Subsequently, 215 parts of metaxylylene diisocyanate (Mitsui Chemical Polyurethane Co., Ltd.) was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 24500 and an actually measured resin solid acid value of 99 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 26300 and an actually measured resin solid acid value of 11 mgKOH / g.

  Next, 63 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the carboxyl group-containing photosensitive urethane resin prepared by this production example is 858 g / eq, the weight average molecular weight in terms of polystyrene is 27400, and the acid value of the resin solid content by actual measurement is It was 67 mgKOH / g.

  Table 1 shows the physical properties of the carboxyl group-containing photosensitive urethane resins obtained in Production Examples 1 to 13.

1) PTG1000 sn: Hodogaya Chemical Co., Ltd .: polytetramethylene glycol 2) DMBA: Nippon Kasei Co., Ltd .: dimethylolbutanoic acid 3) IPDI: isophorone diisocyanate 4) GMA: glycidyl methacrylate 5) SA ... succinic anhydride 6) 4HBAGE ... 4-hydroxybutyl acrylate glycidyl ether 7) TH ... tetrahydrophthalic anhydride 8) OXMA ... oxetanyl methacrylate 9) C-1090 ... manufactured by Kuraray Co., Ltd. : Polycarbonate diol 10) DMPA ... Nippon Kasei Co., Ltd .: dimethylolpropionic acid 11) XDI ... Mitsui Chemicals Polyurethanes Co., Ltd .: Metaxylylene diisocyanate

[Production Example 14]
A 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, bisphenol A type epoxy having an epoxy equivalent of 650, a softening point of 81.1 ° C, and a melt viscosity (150 ° C) of 12.5 poise 371 parts of resin, 925 parts of epichlorohydrin, and 463 parts of dimethyl sulfoxide were added and dissolved uniformly, and then 52.8 parts of 98.5% aqueous sodium hydroxide solution was added at 70 ° C. over 100 minutes with stirring. After the addition, the reaction was further performed at 70 ° C. for 3 hours. Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, the reaction product containing by-product salt and dimethyl sulfoxide is dissolved in 750 parts of methyl isobutyl ketone, and further 10 parts of 30% aqueous sodium hydroxide solution. And reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water. After separation of oil and water, methyl isobutyl ketone is recovered by distillation from the oil layer, and 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. 340 parts were obtained.

  287 parts of this epoxy resin was put into a four-necked flask equipped with another stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer, and further 72 parts of acrylic acid, 0.3 part of methylhydroquinone, cyclohexanone 194 The reaction mixture was dissolved by heating and stirring at 90 ° C. Subsequently, the reaction liquid was cooled to 60 ° C., 1.7 parts of triphenylphosphine was added, and the reaction was performed at 100 ° C. for about 32 hours in the presence of oxygen to obtain a reaction product having an actually measured acid value of 1 mg KOH / g. Next, 78 parts of succinic anhydride and 42 parts of cyclohexanone were added thereto and reacted 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. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the bisphenol A type epoxy resin prepared according to this production example is 450 eq / g, the weight average molecular weight in terms of polystyrene is 7400, and the acid value of the measured resin solid content is 100 mgKOH / g g.

[Production Example 15]
To a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, an inlet tube, and a thermometer, 330 parts of a cresol novolac epoxy resin having an epoxy equivalent of 218 g / eq (manufactured by Toto Kasei Co., Ltd .: YDCN-702). The mixture was melted by heating at 90 to 100 ° C. and stirred. Next, 120 parts of acrylic acid, 0.6 part of hydroquinone, and 5 parts of dimethylbenzylamine were added, and the mixture was heated to 115 ° C. with stirring in the presence of oxygen and reacted for 12 hours. Next, 400 parts of cyclohexanone was added to this flask and dissolved by heating to 70 ° C. Next, 81 parts of succinic anhydride was added, the temperature was raised to 95 ° C., and the mixture was stirred and reacted for 8 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was a cresol novolak skeleton. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the acid anhydride-modified cresol novolak resin prepared by this production example is 319 g / eq, the weight average molecular weight in terms of polystyrene is 11000, and the acid value of the resin solid content by actual measurement is It was 85 mgKOH / g.

[Production Example 16]
A dropping funnel was placed in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, and 400 parts of cyclohexanone was charged into the flask, and the temperature was raised to 90 ° C. with stirring in a nitrogen atmosphere. did. In a separate container, 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 are stirred and dissolved uniformly. did. The monomer solution was charged into a dropping funnel installed in the flask, and the monomer solution in the dropping funnel was dropped into the flask over 2 hours while stirring the flask at 90 ° C. in a nitrogen atmosphere. Stirring was continued at 90 ° C. even after completion of the dropping, and 0.5 part of azobisisobutyronitrile was charged into the flask after 2 hours from the end of the dropping. After 1 hour, 0.5 part of azobisisobutyronitrile was again added to the flask, and stirring was continued for another 2 hours. Thereafter, the flask was cooled to stop the reaction. A small amount of sampling was performed to obtain a carboxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 18700 and an acid value of resin solid content of 98 mgKOH / g.

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

  Next, 63 parts of succinic anhydride was added to the flask and reacted for 6 hours with stirring at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was an acrylic resin. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the acrylic resin prepared by this production example is 863 g / eq, the weight average molecular weight in terms of polystyrene is 22000, and the acid value of the resin solid content measured is 70 mg KOH / g. It was.

[Production Example 17]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer, 212 parts of polytetramethylene glycol (PTG850: Hodogaya Chemical Co., Ltd .: hydroxyl value = 129 mgKOH / g), ethylene glycol 75 Part, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, cyclohexanone 375 parts as a solvent, stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Reaction was performed. Subsequently, 54 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 15200 and an actually measured resin solid acid value of 170 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 110 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling was performed to obtain a carboxyl group-containing photosensitive urethane resin whose main skeleton is an acid anhydride-modified urethane skeleton. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the acid anhydride-modified urethane resin prepared according to this production example is 896 g / eq, the weight average molecular weight in terms of polystyrene is 18800, and the acid value of the resin solid content actually measured is 72 mgKOH / g.

[Production Example 18]
In a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 218 parts of polytetramethylene glycol (PTG850: Hodogaya Chemical Co., Ltd .: hydroxyl value = 129 mgKOH / g), ethylene glycol 47 Part, 125 parts of pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.), 2 parts of dimethylbenzylamine, and 375 parts of cyclohexanone as a solvent, stirred for 10 hours at 100 ° C. with stirring in a nitrogen stream, Reaction was performed. Subsequently, 111 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a carboxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 17000 and an actually measured resin solid acid value of 110 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 131 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing urethane prepolymer having a polystyrene-equivalent weight average molecular weight of 19,200 and an actually measured acid value of resin solid content of 4 mgKOH / g.

  Next, 74 parts of succinic anhydride was added to the flask, and the reaction was further continued for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group disappeared by FT-IR measurement, 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. Next, cyclohexanone was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content of the acid anhydride-modified urethane resin prepared according to this production example is 765 g / eq, the weight average molecular weight in terms of polystyrene is 21400, and the acid value of the resin solid content measured is 67 mg KOH. / G.

  Table 2 summarizes the physical properties of the resins obtained in Production Examples 14 to 18.

[Example 1]
100.0 parts of resin varnish (carboxyl group-containing urethane prepolymer solution) obtained in Production Example 1, Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd .: 2-methyl-1- [4] as a photopolymerization initiator -(Methylthio) phenyl] -2-morpholino-1-propane) 2.5 parts, also DETX-S (Nippon Kayaku Co., Ltd .: 2,4-diethylthioxanthone) 0.25 parts, photosensitive ethylenically unsaturated SR-355 (manufactured by Nippon Kayaku Co., Ltd .: ditrimethylolpropane tetraacrylate) as a group-containing compound was uniformly dissolved and mixed to prepare the photosensitive resin composition of the present invention.

[Examples 2 to 13]
About the resin varnish obtained by manufacture example 2-13, it mix | blended in the ratio similar to Example 1, and created the photosensitive resin composition containing each resin.

[Comparative Examples 1-5]
About the resin varnish obtained by manufacture examples 14-18, it mix | blended in the ratio similar to Example 1, and created the photosensitive resin composition containing each resin.

<Evaluation 1>
The following evaluation was performed about the obtained photosensitive resin composition.
[Create sample A]
The obtained photosensitive resin composition was applied on a polyimide film (Kapton 100H: manufactured by Toray DuPont Co., Ltd .: 25 μm thick) so that the dry film thickness was 20 μm, and dried for 30 minutes in an 80 ° C. hot air dryer. And then cooled to room temperature. This is designated as sample A.

[Create sample B]
Sample A was irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm ² using an ultraviolet exposure device (USHIO INC .: “UVC-2534 / 1MNLC3-AA08”, 120 W / cm metal halide lamp, 1 lamp), and then 150 It was heat-cured (post-cured) for 1 hour in a hot air dryer at 0 ° C. The obtained cured film was cooled to room temperature. This is designated as sample B.

[Create sample C]
21 steps of Step Tablet (manufactured by Kodak Co., Ltd.) were brought into intimate contact with Sample A, and irradiated with ultraviolet rays having an integrated light amount of 150 mJ / cm ² using the same ultraviolet exposure apparatus used when Sample B was prepared. This is designated as sample C.
The step tablet is a light-shielded film so that the optical density is increased sequentially in 21 steps. This is brought into close contact with the test coating, irradiated with light from above the film, and then developed. Depending on the resolution of the coating film, the number of steps of the coating film changes. This serves as an index for evaluating the resolution of the test coating film.

[Evaluation of adhesion]
In accordance with JIS K5400, 100 pieces of cut pieces were made in a 1 mm × 1 mm grid pattern on the cured coating film of Sample B, and a peeling test was performed using cello tape (registered trademark). The peeled state of the grid-like cut pieces was observed and evaluated according to the following criteria.
○: No peeling Δ: 20% or less of the grid cut pieces are peeled ×: 21% or more of the grid cut pieces are peeled

[Evaluation of flexibility]
Sample B was bent 180 degrees with the cured coating surface facing outward, and the coating state at that time was evaluated according to the following criteria.
○: No cracks are observed on the film surface Δ: Slight cracks are observed on the film surface ×: The film is cracked and cracks are clearly seen on the film surface

[Evaluation of developability]
Sample C was developed with a 1% aqueous sodium carbonate solution at a spray pressure of ² Kg / cm ² for 60 seconds. The number of steps in which the coating film was swollen with the developer was defined as the number of swelling steps, and the number of steps in which the coating film was washed away with the developer was defined as the number of peeling steps. It can be said that the lower the number of peeling steps, the faster the development speed and the better the developability. The developability was judged according to the following criteria using the number of peeling steps.
○ ... Number of peeling steps ≦ 10
Δ: number of peeling steps = 11-15
X ... number of peeling steps ≥ 16

[Evaluation of resolution]
With respect to the number of swelling steps and the number of peeling steps confirmed in the evaluation of developability, a resolution step was obtained by the following formula.
[Resolution step] = [number of peeling steps] − [number of swelling steps]
It can be said that the smaller the resolution step, the sharper the pattern can be formed in the actual pattern forming process, and the better the resolution. Using this resolution step, the resolution was judged according to the following criteria.
○ ・ ・ ・ Resolution step ≦ 2
Δ: Resolution step = 3-5
× ・ ・ ・ Resolution step ≧ 6

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

  From the result of evaluation 1, in the prior art (Comparative Examples 1 to 5), those having excellent adhesion and flexibility have poor developability and resolution, and conversely those having excellent developability and resolution have adhesion.・ It was found to be inferior in flexibility. On the other hand, it was found that the resin compositions (Examples 1 to 13) of the present invention are excellent in all properties such as adhesion, flexibility, developability, and resolution.

[Example 14]
100.0 parts of resin varnish (carboxyl group-containing urethane prepolymer solution) obtained in Production Example 1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1- as a photopolymerization initiator Propane (Irgacure 907: Ciba Specialty Chemicals Co., Ltd.) 2.5 parts, 2,4-diethylthioxanthone (DETX-S: Nippon Kayaku Co., Ltd.) 0.25 parts, photosensitive ethylenic unsaturated 7.5 parts of ditrimethylolpropane tetraacrylate (SR-355: manufactured by Nippon Kayaku Co., Ltd.) as the group-containing compound, hydrogenated bisphenol A diglycidyl ether (Denacol EX-252: manufactured by Nagase ChemteX Corporation) as the thermosetting component 15.0 parts was uniformly dissolved and mixed to prepare the photosensitive resin composition of the present invention.

[Examples 15 to 26]
About the resin varnish obtained by manufacture example 2-13, it mix | blended in the ratio similar to Example 14, and created the photosensitive resin composition containing each resin.

[Comparative Examples 6 to 10]
About the resin varnish obtained by manufacture examples 14-18, it mix | blended in the ratio similar to Example 14, and created the photosensitive resin composition containing each resin.

<Evaluation 2>
The following evaluation was performed about the obtained photosensitive resin composition.
[Create sample D]
It processed by the method similar to preparation of the sample A of the evaluation 1, and obtained the dry coating film. This is designated as sample D.

[Create sample E]
Sample D was used in place of sample A, and a cured film was obtained by processing in the same manner as in the preparation of sample B of evaluation 1. This is designated as sample E.

[Create sample F]
Sample D was used in place of sample A, and a cured film was obtained by processing in the same manner as in the preparation of sample C in Evaluation 1. This is designated as sample F.

[Create sample G]
The obtained photosensitive resin composition was applied on a 38 μm-thick polyethylene terephthalate (hereinafter also referred to as “PET”) separator film so as to have a dry film thickness of 20 μm, and 30 ° C. with a hot air dryer at 80 ° C. After being dried for a while, it was cooled to room temperature. Next, evaluation 1. The sample was irradiated with ultraviolet rays having an integrated light amount of 300 mJ / cm ² using the same ultraviolet exposure apparatus used when preparing Sample B, and then heat-cured (post-cure) for 1 hour with a 150 ° C. hot air dryer. The obtained cured film was cooled to room temperature, and the cured coating film was peeled off from the separator film. This is designated as sample G.

[Evaluation of finger touch]
For sample D, tackiness was evaluated by finger touch as follows.
○ ・ ・ ・ No fingerprints △ ・ ・ ・ Slight fingerprints ×× Fingerprints clearly

[Evaluation of adhesion]
Sample E was used in place of sample B, and an adhesion test was conducted and evaluated in the same manner as in evaluation 1.

[Evaluation of flexibility]
A sample E was used in place of the sample B, and a flexibility test was conducted and evaluated in the same manner as in the evaluation 1.

[Evaluation of developability]
A sample F was used in place of the sample C, and a developability test was conducted in the same manner as in the evaluation 1, and the evaluation was performed according to the following criteria.
○ ... number of stripping stages ≤ 7
Δ: number of peeling steps = 8-14
X ... number of peeling steps ≥ 15

[Evaluation of resolution]
Similar to Evaluation 1, the resolution was evaluated according to the following criteria.
○ ・ ・ ・ Resolution step ≦ 3
Δ: Resolution step = 4-7
× ・ ・ ・ Resolution step ≧ 8

[Evaluation of solvent resistance]
Sample E is immersed in isopropyl alcohol for 30 minutes at room temperature. After confirming that there was no abnormality in the appearance, a peeling test using an adhesive tape [Cerotape (registered trademark)] was performed, and evaluation was performed according to the following criteria.
○ ・ ・ ・ There is no abnormality in the appearance of the coating film, and there is no blistering or peeling. Δ ・ ・ ・ Slight peeling at the end of the coating film (between the coated part and the polyimide base material). And there is peeling

[Evaluation of acid resistance]
Sample E is immersed in a 10% aqueous hydrochloric acid solution at room temperature for 30 minutes. After confirming that there was no abnormality in the appearance, a peeling test using an adhesive tape [Cerotape (registered trademark)] was performed, and evaluation was performed according to the following criteria.
○ ・ ・ ・ There are no abnormalities in the appearance of the coating film, and there is no swelling or peeling. △ ・ ・ ・ Slight swelling or peeling is observed around the edge of the coating film (between the coated part and the polyimide substrate).・ There are swelling and peeling on the coating film.

[Evaluation of substrate warpage]
Sample E was cut into a square of 5 cm × 5 cm, and the cured coating film surface was faced up, and was allowed to stand on a flat table at 25 ° C. and a humidity of 50% for 12 hours. For the sample after standing, the height at which the four corners of the square were lifted from the table was measured, the average value was calculated, and evaluated according to the following criteria. The smaller this value, the less the sample warps, indicating better.
○: 5 mm or less Δ ... 6 mm or more to 10 mm or less x ... 11 mm or more

[Evaluation of flexibility]
Sample G was folded 180 degrees and the same part was folded 180 degrees on the opposite side. The state of the coating film at that time was judged according to the following criteria.
○: No cracks are observed on the film surface Δ: Slight cracks are observed on the film surface ×: The film is cracked and cracks are clearly seen on the film surface

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

  From the results of Evaluation 2, the resin compositions (Examples 14 to 26) of the present invention are excellent in adhesion, flexibility, and developability, as well as Evaluation 1, and also have good workability due to less dry film tack. Was also found to be excellent. Furthermore, it has been found that the coating film has the performance that cannot be achieved by the conventional technique (Comparative Examples 6 to 10), which has both the resistance of the coating film and the flexible performance such as substrate warpage and flexibility.

[Example 27]
105 parts of resin varnish (carboxyl group-containing urethane prepolymer solution) obtained in Production Example 1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane (as photopolymerization initiator) Irgacure 907: Ciba Specialty Chemicals Co., Ltd.) 6 parts, 2,4-diethylthioxanthone (DETX-S: Nippon Kayaku Co., Ltd.) 1 part, Trimethylol as photosensitive ethylenically unsaturated group-containing compound 8 parts of propane PO-modified triacrylate (Aronix M-310: manufactured by Toagosei Co., Ltd.), 21 parts of dicyclopentadiene type epoxy (HP7200: manufactured by Dainippon Ink & Chemicals) as thermosetting component, and dicyandiamide (as thermosetting aid) DICY7: Ajinomoto Fine Techno Co., Ltd.) 1 part, loose as additive 3 rolls containing 8 parts of silica fine particles (R812: manufactured by Nippon Aerosil Co., Ltd.) and 2 parts of green paste (green pigment / base resin (phenol resin) / solvent (carbitol acetate) = 28/12/60) The photosensitive solder resist ink of the present invention was prepared by kneading with

[Examples 28 to 39]
About the resin varnish obtained by manufacture example 2-13, it mix | blended in the ratio similar to Example 27, and created the soldering resist ink containing each resin.

[Comparative Examples 11-15]
About the resin varnish obtained by manufacture examples 14-18, it mix | blended in the ratio similar to Example 27, and created the soldering resist ink containing each resin.

[Example 40]
105 parts of resin varnish (carboxyl group-containing urethane prepolymer solution) obtained in Production Example 1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propane (as photopolymerization initiator) Irgacure 907: Ciba Specialty Chemicals Co., Ltd.) 6 parts, 2,4-diethylthioxanthone (DETX-S: Nippon Kayaku Co., Ltd.) 1 part, Trimethylol as photosensitive ethylenically unsaturated group-containing compound 8 parts of propane PO-modified triacrylate (Aronix M-310: manufactured by Toagosei Co., Ltd.), 25 parts of a flexible epoxy resin (EPICLON EXA-4850-150: manufactured by Dainippon Ink and Chemicals) as thermosetting component 1 part of dicyandiamide (DICY7: Ajinomoto Fine Techno Co., Ltd.) as an agent, As additives, 8 parts of hydrophobic silica fine particles (R812: manufactured by Nippon Aerosil Co., Ltd.), 2 parts of green paste (green pigment / base resin (phenol resin) / solvent (carbitol acetate) = 28/12/60), and phosphazene -Based flame retardant (SPB-100: manufactured by Otsuka Chemical Co., Ltd.) 8 parts, melamine polyphosphate (PHOSMEL-100: manufactured by Nissan Chemical Industries, Ltd.) 8 parts, melamine cyanurate flame retardant (STABIACE MC-5S: Sakai Chemical Industry Co., Ltd.) (Company) 8 parts was blended and kneaded with 3 rolls to prepare the photosensitive solder resist ink of the present invention.

[Examples 40 to 52]
About the resin varnish obtained by manufacture example 2-13, it mix | blended in the ratio similar to Example 40, and created the photosensitive soldering resist ink containing each resin.

[Comparative Examples 16 to 20]
About the resin varnish obtained by manufacture examples 14-18, it mix | blended in the ratio similar to Example 40, and created the photosensitive soldering resist ink containing each resin.

<Evaluation 3>
The following evaluation was performed about the obtained photosensitive soldering resist ink.

[Create sample H]
Photosensitive solder resist inks obtained in Examples 21 to 40 and Comparative Examples 11 to 20 so that the film thickness after drying was 20 μm on the release surface of a 38 μm-thick separator PET film on which one side was peeled. And dried for 20 minutes by hot air drying at 80 ° C. Next, the photosensitive resin composition surface on this film and a 25 μm-thick PET film are laminated to create a dry film type photosensitive solder resist of the photosensitive resin composition in which both surfaces are sandwiched by the PET film. did.

Next, from this dry film, the separator PET film is peeled off, and the photosensitive resin composition surface exposed on the surface and the copper foil surface of the copper-clad laminate (thinning the copper surface by etching) are laminated together, It was made to adhere by vacuum lamination (60 ° C., 0.2 MPa = 2 kg / cm ² ). Subsequently, a negative film having a resist pattern [φ70 μm hole, 21 steps, solid line / space = 100/60 (μm / μm)] is brought into close contact with the PET film, and an ultraviolet exposure device (EXM-1201F manufactured by ORC Corporation, short-circuited). (Arc lamp) was used to irradiate ultraviolet rays (400 mJ / cm ² ). Next, the PET film was peeled off, and developed with a 1% sodium carbonate aqueous solution at a spray pressure of ² kg / cm ² for 60 seconds. Thereafter, heat curing was performed for 1 hour with a hot air dryer at 150 ° C. to prepare Sample H.

[Evaluation of solvent resistance]
Sample H was used in place of sample E, and a solvent resistance test was conducted and evaluated in the same manner as in Evaluation 2.

[Evaluation of acid resistance]
Sample H was used in place of sample E, and an acid resistance test was conducted and evaluated in the same manner as in evaluation 2.

[Evaluation of developability]
A sample H was used in place of the sample C, a developability test was conducted in the same manner as in the evaluation 1, and the determination was made according to the following criteria.
○ ... number of stripping stages ≤ 5
Δ: number of peeling steps = 6-10
× ... Number of peeling steps ≥ 11

[Evaluation of resolution]
For sample H, observe the hole of φ70μm with a magnifying glass, measure the diameter of the part where the resist layer is developed and the copper surface is exposed (the part where the hole is opened), and the resolution is based on the following criteria Judging sex. It can be said that the closer the diameter of this hole is to 70 μm, the more faithfully the pattern is formed and the better the resolution.
○ ・ ・ ・ Diameter 60μm or more Δ ・ ・ ・ Diameter 40μm or more to 59μm or less × ・ ・ ・ Diameter 39μm or less

[Evaluation of solder heat resistance]
A rosin flux (manufactured by Asahi Chemical Research Co., Ltd .: SPEEDY FLUX P-550-5) was applied to Sample H and immersed in a solder bath (JIS C 6481) at 260 ° C. for 10 seconds. This was repeated as 2 cycles, and the state of the coating film was determined as follows.
○… There is no abnormality in the appearance of the coating film, and there is no swelling or peeling.
Δ: The coating film is partially swollen or peeled off.
X: The whole coating film has swelling or peeling.

[Create 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 separator PET film so that the dry film thickness was 20 μm, and a hot air drier at 80 ° C. Dry for 20 minutes. Next, after irradiating ultraviolet rays with an integrated light quantity of 400 mJ / cm ² with the same ultraviolet exposure apparatus used when preparing Sample H of Evaluation 3, it was cured with 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 separator film. This is sample I.

[Evaluation of flexibility]
Similar to the evaluation of flexibility in Evaluation 2, Sample I was tested for flexibility and evaluated.

[Create 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 without using a negative film having a resist pattern in the preparation process of Sample H (entire surface) Sample J was prepared in the same manner as Sample H except for (exposure).

[Evaluation of flame retardancy]
Sample J was evaluated for flame retardancy in accordance with the UL Subject 94V method, and the results were judged according to the following criteria.
○ ・ ・ ・ VTM-0
△ ・ ・ ・ VTM-1
× ・ ・ ・ VTM-2 or less (including complete combustion)

<Evaluation results>
The results of Evaluation 3 are shown in Table 5 and Table 6.

  As can be seen from the results in Table 5, in Comparative Examples 11 and 12 (prior art), the coating film resistance, developability and heat resistance are excellent, but the most important as a flexible insulating protective film used for flexible printed wiring boards and the like. The flexibility that is a physical property could not be satisfied. Moreover, in Comparative Examples 13-15 (prior art), it was a result with inferior coating-film resistance and developability instead of being excellent in flexibility. On the other hand, the photosensitive resin composition of the present invention (Examples 27 to 39) was able to satisfy all of these physical properties essential as a flexible insulating protective layer at a high level.

  In particular, the carboxyl group-containing photosensitive urethane resin of the present invention having no ester skeleton derived from half-esterification with an acid anhydride in the main chain is the same urethane main skeleton because the main chain is chemically stable. When compared with Examples 14 and 15, it has a characteristic that it can exhibit adhesion and flexibility specific to urethane resin while maintaining particularly excellent coating film resistance and heat resistance. In addition, the carboxyl group-containing photosensitive urethane resin of the present invention has a photosensitive group and a carboxyl group in the side chain, and thus exhibits very good developability even when the amount of the carboxyl group contained is small. Since the functional group is rich in reactivity compared with the case where it is directly connected to the main chain, it can exhibit excellent resolution and coating film resistance.

As can be seen from the results in Table 6, by adding a flame retardant, the prior art (Comparative Examples 16 to 20) generally decreased the physical properties as a resist, but the photosensitive resin composition of the present invention (Examples). 40-52) was able to achieve both flame retardancy and other physical properties as a resist. This is because the carboxyl group-containing photosensitive urethane resin of the present invention has a photosensitive group and a carboxyl group that are highly reactive in the side chain, as described above, and developability such as a flame retardant and the like. Even when there is a factor that significantly impairs photosensitivity, it exhibits excellent developability and photosensitivity, and can exhibit flame retardancy while maintaining resolution and coating film resistance.
As mentioned above, although this invention was demonstrated along the specific aspect, the deformation | transformation and improvement obvious to those skilled in the art are included in the scope of the present invention.

Claims (11)

A photosensitive resin composition comprising a carboxyl group-containing photosensitive urethane resin (A), a photopolymerization initiator (B), and a photosensitive ethylenically unsaturated group-containing compound (C),
The carboxyl group-containing photosensitive urethane resin (A)
A carboxyl group in a carboxyl group-containing urethane prepolymer (a) obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components; ,
A hydroxyl group in the hydroxyl group-containing urethane prepolymer (c) obtained by reacting an epoxy group or oxetane group in the compound (b) having an epoxy group or oxetane group and an ethylenically unsaturated group;
A photosensitive resin composition, which is a resin obtained by reacting an acid anhydride group in an acid anhydride group-containing compound (d).   Furthermore, the photosensitive resin composition of Claim 1 containing a thermosetting compound (D).   Furthermore, the photosensitive resin composition of Claim 2 containing a thermosetting auxiliary agent (E).   The photosensitive resin composition according to any one of claims 1 to 3, wherein the acid value of the carboxyl group-containing photosensitive urethane resin (A) is 10 to 200 mgKOH / g.   The photosensitive resin composition according to any one of claims 1 to 4, wherein the carboxyl group-containing photosensitive urethane resin (A) has an ethylenically unsaturated group equivalent of 200 to 3000 g / eq.   The photosensitive resin composition according to any one of claims 1 to 5, 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 according to any one of claims 2 to 6, wherein the thermosetting compound (D) is a compound (k) having two or more epoxy groups or oxetane groups.   Hardened | cured material formed by hardening | curing the photosensitive resin composition in any one of Claims 1-7.   The photosensitive soldering resist ink containing the photosensitive resin composition in any one of Claims 1-7, and a flame retardant.   A dry film type photosensitive solder resist comprising the photosensitive resin composition according to claim 1 and a flame retardant. First, a carboxyl group-containing urethane prepolymer (a) is obtained by reacting a polymer polyol (e), a carboxylic acid compound (f) having two hydroxyl groups in the molecule, and a diisocyanate compound (g) as essential components. The process of
Second step of obtaining a hydroxyl group-containing urethane prepolymer (c) by reacting the carboxyl group-containing urethane prepolymer (a) with a compound (b) having an epoxy group or an oxetane group and an ethylenically unsaturated group. ,
And the manufacturing method of the carboxyl group-containing photosensitive urethane resin characterized by including the 3rd process with which the said hydroxyl-containing urethane prepolymer (c) and an acid anhydride group containing compound (d) are made to react.