KR101174981B1 - Curable resin composition, and dry film and printed wiring board using the same - Google Patents

Abstract

The present invention is a curable resin composition containing a halogen-free flame retardant, a curable resin composition capable of forming a solder resist layer having low deformation resistance and excellent in flame retardancy and bendability, a dry film thereof, and flame retardancy such as a solder resist by these. Provided is a printed wiring board on which a cured coating of is formed.
Curable resin composition of this invention contains (A) carboxyl group-containing resin, (B) aluminum hydroxide, and (C) spherical silica. In addition to each of the above components, by containing a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in the molecule (D), a thermosetting resin composition can be obtained, and further (F) photopolymerization initiator and (G) By containing a photopolymerizable monomer, it can be set as the photocurable thermosetting resin composition. Preferably, it further contains (E) phosphorus containing compound.

Description

Curable resin composition, dry film and printed wiring board using the same {CURABLE RESIN COMPOSITION, AND DRY FILM AND PRINTED WIRING BOARD USING THE SAME}

This invention relates to curable resin composition, especially curable resin composition which has low deformation | transformation and can form the soldering resist excellent in flame retardancy and bendability. Moreover, this invention relates to the dry film which used such curable resin composition, and a flame-retardant printed wiring board.

Background Art Conventionally, printed wiring boards and flexible wiring boards (hereinafter, abbreviated as FPCs) have been required for flame retardancy in order to be mounted on electronic devices, and flame retardancy is also required for solder resists which are a part of them. Among these, since FPC usually contains a polyimide substrate, it is a thin film unlike the printed wiring board of a glass epoxy substrate. However, since the solder resist to be applied has the same film thickness of both the printed wiring board and the FPC, in the case of the FPC of the thin film, the burden of flame retardation to the solder resist becomes relatively large.

Therefore, various proposals have been made regarding flame retardation of a soldering resist conventionally. For example, Japanese Patent Laid-Open No. 2007-10794 (Patent Document 1) discloses polymerizable ethylenic compounds such as halogenated aromatic rings such as (a) binder polymers, (b) bromophenyl groups, and (meth) acryloyl groups. A flame-retardant photosensitive resin composition for FPC containing a photopolymerizable compound having an unsaturated bond in a molecule, (c) a photopolymerization initiator, (d) a block isocyanate compound, and (e) a phosphorus-containing compound having a phosphorus atom in a molecule has been proposed. . However, the use of halogen compounds such as compounds having unsaturated double bonds polymerizable with halogenated aromatic rings is undesirable from the viewpoint of environmental load.

Therefore, in recent years, in view of reducing environmental load, instead of the conventional green colorant chlorinated phthalocyanine green, a solder resist using phthalocyanine blue and a yellow colorant having no halogen atom has been widely used (for example, in the patent literature). 2). In addition, phthalocyanine blue is used to clearly claim that it is halogen-free in appearance, and is also used as a blue solder resist. However, the solder resist is formed to protect the copper circuit, but one of the roles is that the heat and moisture of the copper circuit, electrical discoloration, damage on the copper circuit, contamination, etc. are also not observed. . On the other hand, addition of a coloring agent is normally performed about a soldering resist, and it makes it hard to observe an external defect by increasing the density | concentration. However, when the blue solder resist ink or the green solder resist ink using the blue colorant and the yellow colorant is weaker than the green color due to the phthalocyanine green, the concealability is weak and the function as a colorant that makes it difficult to observe appearance defects cannot be sufficiently performed. There is.

Moreover, in the printed circuit board of the thin film represented by FPC, generation | occurrence | production of the deformation | transformation by hardening shrinkage at the time of photocuring or thermosetting of a soldering resist becomes a problem.

On the other hand, aluminum hydroxide is a flame retardant filler, and it is known that the composition becomes flame retardant as it adds in a resin composition. However, there is a problem that the shape of aluminum hydroxide is indefinite, and excessive addition causes cracking at the interface between aluminum hydroxide and the resin and lowers the bending resistance of the cured film. Therefore, the addition amount was restrict | limited to the printed wiring board which especially bendability is required, especially the soldering resist for FPC board | substrates.

As a method for preventing interfacial cracking of organic and inorganic materials, a method of improving the affinity of inorganic particles such as fillers for organic materials is known, and silane coupling agent treatment, titanate and aluminum chelate treatment have been conventionally performed. However, these affinity improvement methods have little effect on aluminum hydroxide, and the reality is that almost no improvement effect on bending of the cured film is obtained.

Japanese Patent Laid-Open No. 2007-10794 (claims) Japanese Patent Laid-Open No. 2000-7974 (claims)

The present invention has been made to solve the problems of the prior art as described above, and its main object is a curable resin composition containing a halogen-free flame retardant, and has a low deformation and forms a solder resist layer resistant to bending. It is to provide possible curable resin composition.

Moreover, the objective of this invention is providing the printed wiring board which has a low deformation | transformation, is excellent in flame retardancy and bendability, and has a flame-retardant film of such excellent characteristics by using such a curable resin composition.

In order to achieve the above object, according to the present invention, there is provided a curable resin composition comprising (A) carboxyl group-containing resin, (B) aluminum hydroxide and (C) spherical silica.

In one aspect, it can be set as a thermosetting resin composition by containing the thermosetting component which has 2 or more cyclic ether group and / or cyclic thioether group in (D) molecule further in addition to each said component. In another preferable aspect, (E) phosphorus containing compound is further contained. In another aspect, it can be set as photocurable thermosetting resin composition by containing (F) photoinitiator and (G) photopolymerizable monomer further. In another preferable aspect, it further contains a coloring agent (H). In a more preferred embodiment, the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane structure, or a carboxyl group-containing resin having a biphenyl novolak structure and an ethylenically unsaturated group, and at least two cyclic ether groups in the molecule and / or Or the thermosetting component (D) having a cyclic thioether group is an epoxy resin having a biphenyl novolak skeleton. Such curable resin composition can be used suitably for soldering resist formation of a printed wiring board.

Moreover, according to this invention, the thermosetting and / or photocuring of the dry film obtained by apply | coating and drying the said curable resin composition to a film, or the dry film obtained by apply | coating and drying the said curable resin composition or this curable resin composition to a carrier film is carried out. The hardened | cured material obtained by providing is provided. Moreover, according to this invention, the printed wiring board which has the said hardened | cured material is also provided.

Curable resin composition of this invention contains (A) aluminum hydroxide and (C) spherical silica together with (A) carboxyl group-containing resin, Preferably it contains (E) phosphorus containing compound, and is a non-halogen composition It has a low environmental load and is flame retardant, and can form a film having excellent low deformation and bendability. Therefore, by using the curable resin composition of this invention, the printed wiring board which has a low deformation | transformation, is excellent in flame retardancy and bendability, and has a flame-retardant soldering resist film of such an outstanding characteristic can be provided.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, as a result of mix | blending a spherical silica (C) with a carboxyl group-containing resin (A) with aluminum hydroxide (B) as a flame-retardant filler, while maintaining the flame retardance of curable resin composition, It has been found that the bending resistance can be improved. Particularly, since the spherical silica did not have a surface which is a starting point of cracking of the cured film, it had an effect of improving bending resistance by itself. Moreover, the surface treatment by a silane coupling agent etc. acted very effectively with respect to silica, and was able to drastically improve bending resistance. This effect was a surprising effect that was never conceived before.

Hereinafter, each structural component of curable resin composition of this invention is demonstrated in detail.

As carboxyl group-containing resin (A) contained in curable resin composition of this invention, the well-known conventional resin compound which contains a carboxyl group in a molecule | numerator can be used. Moreover, when it is set as alkali developable resin composition, carboxyl group-containing photosensitive resin (A ') which has an ethylenically unsaturated double bond in a molecule | numerator is more preferable at the point of photocurability and developability. In addition, the unsaturated group is preferably derived from an acrylic acid or methacrylic acid derivative. In addition, when using only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, it is necessary to use together the photopolymerizable monomer (G) which has two or more ethylenically unsaturated groups in the molecule mentioned later. have.

As a specific example of carboxyl group-containing resin (A), the compound (it may be any of an oligomer and a polymer) listed below can be used preferably.

(1) Carboxyl group-containing resin obtained by copolymerization of unsaturated carboxylic acids, such as (meth) acrylic acid, and unsaturated group containing compounds, such as styrene, (alpha) -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

(2) diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid; and polycarbonate polyols and polyethers. Carboxyl group containing by polyaddition reaction of diol compounds, such as a compound polyol, a polyester type polyol, a polyolefin type polyol, an acryl type polyol, a bisphenol A alkylene oxide adduct diol, a compound which has a phenolic hydroxyl group and an alcoholic hydroxyl group, etc. Urethane resin.

(3) diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol Terminal carboxyl group-containing urethane resin which makes acid anhydride react with the terminal of the urethane resin by the polyaddition reaction of diol compounds, such as a compound which has a bisphenol-A alkylene oxide adduct diol, a phenolic hydroxyl group, and an alcoholic hydroxyl group. .

(4) bifunctional epoxy resins such as diisocyanate, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin The photosensitive carboxyl group-containing urethane resin by the polyaddition reaction of the (meth) acrylate or its partial acid anhydride modified substance, carboxyl group-containing dialcohol compound, and diol compound.

(5) In the synthesis | combination of resin of said (2) or (4), the compound which has one hydroxyl group and 1 or more (meth) acryloyl group in the molecule | numerators, such as hydroxyalkyl (meth) acrylate, is added, and the terminal (Meth) acrylated carboxyl group-containing urethane resin.

(6) Having one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate during synthesis of the resin of the above (2) or (4) The carboxyl group-containing urethane resin which added the compound and was terminal (meth) acrylated.

(7) (meth) acrylic acid is made to react with the polyfunctional (solid) epoxy resin as mentioned later, and dibasic acid anhydrides, such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride, were added to the hydroxyl group which exists in a side chain. Photosensitive carboxyl group-containing resin.

(8) Contains photosensitive carboxyl group in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin further epoxidized with epichlorohydrin and a hydroxyl group of a bifunctional (solid) epoxy resin is added to the resulting hydroxyl group. Suzy.

(9) The carboxyl group-containing polyester resin which made dicarboxylic acid react with the bifunctional oxetane resin as mentioned later, and added the dibasic acid anhydride to the produced | generated primary hydroxyl group.

(10) In addition to the resins of the above (1) to (9), one epoxy group and one or more (meth) in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, etc. Photosensitive carboxyl group-containing resin formed by adding the compound which has acryloyl group.

Among these carboxyl group-containing resins, preferred are (X) carboxyl group-containing polyurethane resins, in particular those in which isocyanate groups of components (including diisocyanates) having an isocyanate group of the urethane resin are not directly bonded to the benzene ring, and (Y) the above. When the polyfunctional epoxy resin used for the synthesis of the resin is a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenyl novolak structure, a bissilenol structure, especially a compound having a biphenyl novolak structure and a hydrogenated compound thereof It is preferable at the point of low deformation, bending resistance. In addition, in another aspect, the modified substances such as (2), (3), (4), (5), (6) and (10) are preferable against deformation since they have a urethane bond in the main chain. . Moreover, since resins other than (1), (2), and (9) have a photosensitive group in a molecule | numerator, it is preferable at the point that photoreactivity is high.

Further, in the present specification, the term (meth) acrylate is generically referred to as acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

Since carboxyl group-containing resin (A) mentioned above has many free carboxyl groups in the side chain of a frame | skeleton and a polymer, it becomes a crosslinking point at the time of thermosetting. In addition, when it is set as the photocurable resin composition, image development by a rare alkali aqueous solution is attained.

The acid value of the carboxyl group-containing resin (A) is preferably in the range of 30 to 200 mgKOH / g, more preferably in the range of 40 to 200 mgKOH / g, particularly preferably in the range of 45 to 120 mgKOH / g. desirable. From the viewpoint of alkali developability, alkali development becomes difficult when the acid value of the carboxyl group-containing resin is less than 30 mgKOH / g. On the other hand, when it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary. In some cases, it is not preferable because it is dissolved and peeled off with a developer without distinguishing between the exposed portion and the unexposed portion, and it is difficult to draw a normal resist pattern.

Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeleton, it is preferable to exist in the range of 2,000-150,000 normally, and also 5,000-100,000. When the weight average molecular weight is less than 2,000, the tack-free performance may decrease, the moisture resistance of the coating film after exposure deteriorates, the film decreases at the time of image development, and the resolution may fall large. On the other hand, when a weight average molecular weight exceeds 150,000, developability may deteriorate remarkably and storage stability may fall.

The compounding quantity of carboxyl group-containing resin (A) as mentioned above is 5-60 mass% in the whole composition, Preferably it is 10-60 mass%, More preferably, it is 20-60 mass%, Especially preferably, it is 30-50 mass %to be. When less than the said range, since coating film strength falls, it is unpreferable. On the other hand, when more than the said range, since the viscosity of a composition becomes high, applicability | paintability, etc. fall, it is not preferable.

As aluminum hydroxide (B), a commercially available thing can be used as it is. As a commercial item, the Showa Denko company Heidilite series, HW, H21, H31, H32, H42M, H43M, etc. are mentioned, for example. In addition, since the fine particle diameter of aluminum hydroxide is effective for bending resistance, the particle size of aluminum hydroxide is dispersed and processed beforehand to the primary particle size with a bead mill or the like together with a solvent or a resin. It is preferable from the viewpoint of the flame retardancy and the bendability of the cured film obtained by using.

As for the compounding quantity of these aluminum hydroxide (B), the range of 1-200 mass parts is preferable with respect to 100 mass parts of said carboxyl group-containing resin (A), Preferably it is 1-150 mass parts, More preferably, it is 10-100 mass parts to be.

As the spherical silica (C), commercially available spherical silica having an average particle diameter of 0.25 µm, 0.5 µm, 1 µm, 1.5 µm, 2 µm, 3 µm, 5 µm or the like can be used as it is. Commercially available products include ADMA TECHNOLOGY SO series. Moreover, although a silane coupling agent etc. can also be mix | blended directly with the composition which mix | blended this spherical silica, A solvent, a silane coupling agent, and a spherical silica are surface-treated previously with a bead mill, and a silane coupling agent is uniform to a silica surface. It is preferable from the viewpoint of bendability that it disperse | distributes so that it may be processed, and the thing which filtered and filtered the particle | grains of 5 micrometers or more by filtration etc. may be used.

As for the compounding quantity of these spherical silica (C), the range of 1-200 mass parts is preferable with respect to 100 mass parts of said carboxyl group-containing resin (A), Preferably it is 1-150 mass parts, More preferably, it is 5-100 mass parts It is wealth.

As the thermosetting component (D) used for the purpose of forming the composition of the present invention into a thermosetting resin composition to improve properties such as heat resistance and insulation reliability, two or more cyclic ether groups in a molecule capable of reacting with a carboxyl group of a carboxyl group-containing resin. And / or any conventionally known compound having a cyclic thioether group (hereinafter, abbreviated as cyclic (thio) ether group) can be used. Among them, a bifunctional or higher epoxy resin is preferable in terms of heat resistance and gold plating resistance. In particular, epoxy resins having a biphenyl novolak skeleton are preferred because of their improved heat resistance, gold plating resistance and flame retardancy. As an epoxy resin which has a biphenyl novolak skeleton, Nihon Kayaku Co., Ltd. product NC-3000L, NC-3000, NC-3000H, NC-3100, etc. are mentioned, for example.

In addition, the thermosetting component which has a 2 or more cyclic (thio) ether group in the molecule | numerator which can be used as a thermosetting component in the thermosetting resin composition of this invention is in a 3, 4 or 5-membered ring cyclic ether group or cyclic thioether group in a molecule | numerator. A compound having two or more of any one or two kinds of groups, for example, a compound having two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound (D-1), a compound having two or more oxetanyl groups in a molecule, That is, a polyfunctional oxetane compound (D-2), the compound which has 2 or more thioether group in a molecule | numerator, ie, episulfide resin (D-3), etc. are mentioned.

Examples of the polyfunctional epoxy compound (D-1) include jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin Co., Ltd., Epikron 840, Epikron 850, Epikron 1050, Epikron 2055, Doto Esotto YD-011, YD-013, YD-127, YD-128 by Kasei Co., Ltd., DER317, DER331, DER661, DER664 by Dow Chemical Co., Ltd., Araldide 6071 by Ciba Specialty Chemicals Co., Ltd. , Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Kagaku Kogyo Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, AER of Asahi Kasei Kogyo Co., Ltd. Bisphenol A type epoxy resins such as 330, AER331, AER661, and AER664 (both trade names); JERYL903 made in Japan epoxy resin company, epicron 152 made in DIC company, epicron 165, dopot Kasei Co., Ltd. YPOTT YDB-400, YDB-500, Dow Chemical company's DER542, Ciba specialty chemicals company Brominated epoxy resins such as Araldide 8011, Sumitomo Kagaku Kogyo Co., Ltd. Sumi-Epoxy ESB-400, ESB-700, Asahi Kasei Kogyo Co., Ltd. AER711, AER714 and the like (both trade names); JER152, jER154 manufactured by Japan epoxy resin company, DEN431, DEN438 manufactured by Dow Chemical Company, epicron N-730, epicron N-770, manufactured by DIC Corporation, epicron N-865, manufactured by Toto Kasei Co., Ltd. YDCN-701, YDCN-704, Araldide ECN1235, Araldide ECN1273, Araldide ECN1299, Araldide XPY307 manufactured by Ciba Specialty Chemicals, EPPN-201, EOCN-1025 manufactured by Nihon Kayaku Co., EOCN- Furnace of 1020, EOCN-104S, RE-306, Sumitomo Kagaku Kogyo Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, Asahi Kasei Kogyo AERECN-235, ECN-299 (all brand names) Ballac type epoxy resins; Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Japan Epoxy Resin Corporation, Efotot YDF-170, YDF-175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, Inc. (all brand names) Bisphenol F type epoxy resin; Hydrogenated bisphenol A epoxy resins, such as Efotot ST-2004, ST-2007, and ST-3000 (brand name) by a Toto Kasei company; JER604 made in Japan epoxy resin company, Etoport YH-434 made by Toto Kasei Co., Ltd. Araldide MY720 made by Ciba specialty chemicals company, Sumitomo Kagaku Kogyo Co., Ltd. sumi-epoxy ELM-120 (all brand names) Glycidyl amine epoxy resins; Hydantoin type epoxy resins, such as Araldide CY-350 (brand name) by the Ciba Specialty Chemicals company; Alicyclic epoxy resins such as Celoxide 2021 manufactured by Daicel Chemical Industries, Ltd., Araldide CY175 manufactured by Ciba Specialty Chemicals, and CY179 (both trade names); Trihydroxyphenylmethane type epoxy resins such as YL-933 manufactured by Japan Epoxy Resin Co., Ltd., T.E.N., EPPN-501, EPPN-502, etc. manufactured by Dow Chemical Company; Bixylenol type or biphenol type epoxy resins, such as YL-6056, YX-4000, and YL-6121 (all are brand names) by the Japan epoxy resin company, or mixtures thereof; Bisphenol S type epoxy resins, such as EBPS-200 by Nihon Kayaku Co., Ltd. EPX-30 by Asahi Denka Kogyo Co., Ltd., and EXA-1514 (brand name) by Dainippon Ink & Chemicals Co., Ltd .; Bisphenol A novolak-type epoxy resins, such as jER157S (brand name) by the Japan epoxy resin company; Tetraphenylolethane type epoxy resins, such as jERYL-931 by the Japan epoxy resin company, Araldide 163 by Ciba Specialty Chemicals, Inc. (all are brand names); Heterocyclic epoxy resins, such as Araldide PT810 by Ciba Specialty Chemicals Co., Ltd. and TEPIC by Nissan Chemical Industries, Ltd. (all are brand names); Diglycidyl phthalate resins such as Bremmer DGT manufactured by Nippon Yushi Corporation; Tetraglycidyl xylenoylethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Naphthalene group-containing epoxy resins such as Shin-Netsu Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700; Epoxy resins having a dicyclopentadiene skeleton, such as HP-7200 and HP-7200H manufactured by DIC Corporation; Glycidyl methacrylate copolymer epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Corporation; Copolymerized epoxy resins of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (e.g., YR-102, YR-450, manufactured by Toto Kasei Co., Ltd.), etc. It is not limited to these. These epoxy resins can be used individually or in combination of 2 or more types.

Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1 , 4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3- Oxetanyl) methylacrylate, (3-ethyl-3-oxetanyl) methylacrylate, (3-methyl-3-oxetanyl) methylmethacrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl methacrylate and oligomers or copolymers thereof, oxetane alcohols and novolac resins, poly (p-hydroxystyrene), cardo-type bisphenols, calix arenes and calyx rezos And etherates of resins having hydroxyl groups such as lecinarene or silsesquioxane. In addition, the copolymer etc. of the unsaturated monomer which has an oxetane ring, and an alkyl (meth) acrylate are mentioned.

As episulfide resin (D-3) which has two or more cyclic thioether group in the said molecule | numerator, bisphenol-A episulfide resin YL7000 by the Japan epoxy resin company, etc. are mentioned, for example. Moreover, the episulfide resin etc. which substituted the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom can also be used using the same synthesis method.

The amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2.5 equivalents, more preferably 0.6 to 2.5 equivalents, with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. It is in the range which becomes 0.8-2.0 equivalent. When the compounding quantity of the thermosetting component (D) which has two or more cyclic (thio) ether group in a molecule | numerator is less than 0.6, since a carboxyl group remains in a soldering resist film and heat resistance, alkali resistance, electrical insulation, etc. fall, it is unpreferable. On the other hand, when it exceeds 2.5 equivalent, since low-molecular-weight cyclic (thio) ether group remains in a dry coating film, since the intensity | strength of a coating film, etc. fall, it is unpreferable.

Curable resin composition of this invention is an object for further improving the heat resistance and insulation reliability of a cured coating film, In addition to the thermosetting component (D) which has 2 or more cyclic (thio) ether group in the said molecule, 2 or more isocyanate groups in 1 molecule or Known and commonly used thermosetting resins such as amine resins, cyclocarbonate compounds, bismaleimides, oxazine compounds, oxazoline compounds, carbodiimide resins such as compounds having a blocked isocyanate group, melamine resins, melamine derivatives and benzoguanamine resins Can be blended.

As the compound having two or more isocyanate groups or blocked isocyanate groups in the above one molecule, a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or a compound having two or more blocked isocyanate groups in one molecule, that is, a block isocyanate compound Etc. can be mentioned.

As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer are mentioned. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Moreover, the adduct body, biuret body, and isocyanurate body of the said isocyanate compound are mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the blocking agent dissociates to form an isocyanate group.

As a block isocyanate compound, the addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, an isocyanurate type, a biuret type, an adduct type, etc. are mentioned. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate include the above compounds.

As an isocyanate blocking agent, For example, phenol type blocking agents, such as phenol, cresol, xylenol, chlorophenol, and ethyl phenol; lactam block agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; Methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, glycol Alcohol blocking agents such as butyl acid, diacetone alcohol, methyl lactate, and ethyl lactate; Oxime blocking agents such as formaldehyde doxime, aceto aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; Acid amide-based blocking agents such as amide acetate and benzamide; Imide block agents such as succinic acid imide and maleic acid imide; Amine blocking agents such as xyldine, aniline, butylamine and dibutylamine; Imidazole blockers such as imidazole and 2-ethylimidazole; And imine-based blocking agents such as methyleneimine and propyleneimine.

Block isocyanate compounds may be commercially available, for example, smidule BL-3175, BL-4165, BL-1100, BL-1265, DeathModule TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Death Moss 2170, Des Moss 2265 (above, Sumitomo Bayer urethane company make, brand name), colonate 2512, colonate 2513, colonate 2520 (more, Nippon Polyurethane high school company make, brand name), B-830, B-815 , B-846, B-870, B-874, B-882 (made by Mitsui Tadada Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (manufactured by Asahi Kasei Chemicals Co., Ltd., trade names) Can be. In addition, the smead BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

The compound which has two or more isocyanate groups or blocked isocyanate groups in said 1 molecule can be used individually by 1 type or in combination of 2 or more types.

As for the compounding quantity of the compound which has two or more isocyanate groups or blocked isocyanate groups in such 1 molecule, the ratio of 1-100 mass parts, More preferably, 2-70 mass parts is suitable with respect to 100 mass parts of said carboxyl group-containing resin (A). . When the said compounding quantity is less than 1 mass part, since the toughness of sufficient coating film is not obtained, it is not preferable. On the other hand, when it exceeds 100 mass parts, since the storage stability of a composition falls, it is unpreferable.

Moreover, as another thermosetting component, a melamine derivative, a benzoguanamine derivative, etc. are mentioned. For example, a methylol melamine compound, a methylol benzoguanamine compound, a methylol glycoluril compound, a methylol urea compound, etc. are mentioned. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound are each methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound It is obtained by converting the methylol group of to an alkoxy methyl group. It does not specifically limit about the kind of this alkoxy methyl group, For example, it can be set as a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, butoxymethyl group. Particularly preferred are melamine derivatives having a formalin concentration of 0.2% or less that is friendly to humans and the environment.

As these commercial items, for example, Cymel 300, East 301, East 303, East 370, East 325, East 327, East 701, East 266, East 267, East 238, East 1141, East 272, East 202, East 1156 , Copper 1158, copper 1123, copper 1170, copper 1174, copper UFR65, copper 300 (above, Mitsui Cyanamid Co., Ltd.), Nikalac Mx-750, copper Mx-032, copper Mx-270, copper Mx- 280, Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw- 100 LM, Mw-750 LM (above, Sanwa Chemical Co., Ltd.), etc. are mentioned. The said thermosetting component can be used individually or in combination of 2 or more types.

When using the thermosetting component (D) which has a 2 or more cyclic (thio) ether group in the said molecule, it is preferable to contain a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine Hydrazine compounds, such as a compound, adipic dihydrazide, and sebacic acid dihydrazide; As what is marketed, such as phosphorus compounds, such as a triphenyl phosphine, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are brand names of an imidazole type compound) by the Shikoku Kasei Kogyo Co., Ltd., and an acid apro U-CAT (registered trademark) 3503N, U-CAT3502T (both trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof) Can be mentioned. It does not specifically limit to these, It may be what accelerates reaction of the thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and / or an oxetanyl group, and a carboxyl group, and can also be used individually or in mixture of 2 or more types. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid S-triazine derivatives, such as an adduct, can also be used, Preferably, the compound which functions also as these adhesive imparting agents is used together with the said thermosetting catalyst.

The compounding quantity of these thermosetting catalysts is sufficient in a normal quantity ratio, For example, Preferably it is 0.1-20 mass parts, More preferably, it is 0.5-15.0 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A).

It is preferable that curable resin composition of this invention contains a phosphorus containing compound (E). As a phosphorus containing compound, a conventionally well-known thing is preferable as an organic phosphorus flame retardant, A phosphate ester, a condensed phosphate ester, a cyclic phosphazene compound, a phosphazene oligomer, a phosphinate, or the compound represented by following formula (1) is mentioned.

(Wherein R ¹ , R ² and R ³ each independently represent a substituent other than a halogen atom)

As a commercial item of the compound represented by the said Formula (1), HCA, SANKO-220, M-ESTER, HCA-HQ (all are brand names of Sanko Corp.), etc. are mentioned.

Particularly preferred phosphorus-containing compounds (E) used in the present invention include those having (1) an acrylate group as the reactive group, (2) those having a phenolic hydroxyl group, (3) oligomers or polymers, and (4) phosphazene oligomers. And (5) phosphinates.

(1) Phosphorus-containing compound having an acrylate group

The phosphorus element-containing acrylate has a phosphorus element, preferably a compound containing two or more (meth) acrylates in the molecule, specifically, R ¹ and R ² in the formula (1) are hydrogen atoms, R ³ The compound which is this acrylate derivative can be mentioned, Generally, it synthesize | combines by the Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphafaphenanthrene-10-oxide and a well-known conventional polyfunctional acrylate monomer. can do.

As said commonly used acrylate monomer, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric alcohols such as ethylene oxide adducts, propylene oxide adducts or caprolactone adducts Rates; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; And polyhydric acrylates of glycidyl ethers such as urethane acrylates, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate of the above polyalcohols. ; And melamine acrylate and / or each methacrylate corresponding to the said acrylate etc. are mentioned.

(2) Phosphorus-containing compound having phenolic hydroxyl group

The phosphorus containing compound which has this phenolic hydroxyl group has high hydrophobicity and heat resistance, there is no fall of the electrical property by hydrolysis, and high solder heat resistance. Moreover, as a preferable combination, since it reacts with an epoxy resin and is accommodated in a network by using the epoxy resin or other epoxy resin which has a biphenyl skeleton as (D) component, the advantage that it does not bleed out after hardening is acquired. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.

(3) oligomers or polymers

The phosphorus containing compound which is an oligomer or a polymer has the advantage that there is little fall of bendability under the influence of an alkyl chain, and there is no bleeding-out after hardening because a molecular weight is large. Commercially available products include Sanko Co., Ltd. M-Ester-HP, Toyobo Co., Ltd. phosphorus containing Viron 337, and the like.

(4) phosphazene oligomers

As the phosphazene oligomer, a phenoxy phosphazene compound is effective, and there are substituted or unsubstituted phenoxy phosphazene oligomers or terpolymers, tetramers, and pentamers, and although they are liquid or solid powders, all can be preferably used. . Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Seiyakusho Co., Ltd. Among these, phenoxy phosphazene oligomers substituted with an alkyl group or a polar group such as a hydroxyl group or a cyano group are preferable because they have high solubility in a carboxyl group-containing resin and do not have problems such as recrystallization even when added in large amounts.

(5) phosphinates

By using phosphinate, flame retardance can be improved further, without impairing the cured coating film flexibility. In addition, by using phosphinate excellent in heat resistance, the bleeding out of the flame retardant can be suppressed in the heat press during mounting. Examples of commercially available products include EXOLIT OP930, EXOLIT OP935 manufactured by Clariant.

As for the compounding quantity of the phosphorus containing compound (E) as these flame retardants, the range of 0-200 mass parts is preferable with respect to 100 mass parts of said carboxyl group-containing resin (A), Especially preferably, it is 0-100 mass parts. If it mix | blends in a large amount more than this, since the bending characteristic etc. of the obtained cured film deteriorate, it is unpreferable.

As a photoinitiator (F) which comprises the photocurable resin composition of this invention, 1 selected from the group which consists of an oxime ester system photoinitiator which has an oxime ester group, the (alpha)-amino acetophenone system photoinitiator, and the acylphosphine oxide type photoinitiator It is possible to use more than one kind of photopolymerization initiator.

Examples of commercially available oxime ester photopolymerization initiators include CGI-325, Irgacure-OXE01, Irgacure-OXE02, Adeka N-1919, and Adeka Acruise NCI-831 manufactured by Ciba Specialty Chemicals.

Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used preferably, Specifically, the oxime ester compound which has the carbazole structure represented by following General formula (2) is mentioned.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkyl group having 1 to 8 carbon atoms) Substituted by an alkylamino group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, or an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group) And Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, Substituted by an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group) Substituted with an alkyl group or a dialkylamino group having an alkyl group having 1 to 8 carbon atoms), an anthryl group, a pyridyl group, a benzofuryl group and a benzothienyl group, Ar is an alkylene having 1 to 10 carbon atoms, Vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2 '-Styrene-diyl, n is an integer of 0 or 1)

In particular, in Formula 2, X and Y are each methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene.

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-buta Non, N, N-dimethylamino acetophenone etc. are mentioned. Examples of commercially available products include Irgacure-907, Irgacure-369 and Irgacure-379 manufactured by Ciba Specialty Chemicals.

As an acyl phosphine oxide type photoinitiator, 2,4,6- trimethyl benzoyl diphenyl phosphine oxide, bis (2,4,6- trimethyl benzoyl)-phenyl phosphine oxide, bis (2, 6- dimethoxy specifically, Benzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. As a commercial item, Lucirin TPO by BASF Corporation, Irgacure-819 by Ciba Specialty Chemicals Corporation, etc. are mentioned.

Particularly preferred among the above-described photopolymerization initiators are acylphosphine oxide-based initiators, which have the best light transmittance from the photo bridge performance and are effective in flame retardancy. In addition, since the oxime ester initiator is excellent in initiator efficiency and effective in improving the sensitivity even in a small amount, it is preferable because there is little outgas during heat treatment after forming the resist film, and it is effective for reducing the deformation of the film. Particularly preferred is a combination of both.

As for the compounding quantity of photoinitiator (F) mentioned above, 0.01-30 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), Preferably the range of 0.5-15 mass parts is suitable. If the compounding quantity of a photoinitiator (F) is less than 0.01 mass part, since photocurability on copper is inadequate, a coating film peels off or coating film properties, such as chemical resistance, fall, it is unpreferable. On the other hand, when it exceeds 30 mass parts, since the light absorption on the surface of the soldering resist coating film of a photoinitiator (F) increases, deep-curing property tends to fall, it is unpreferable.

In addition, in the case of the oxime ester type photoinitiator which has group represented by the said Formula (2), the compounding quantity becomes like this. Preferably it is 0.01-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, it is 0.01-5 mass Negative ranges are preferred.

In addition, as a photoinitiator, a photoinitiator, and a sensitizer which can be used suitably for the photocurable resin composition of this invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, A xanthone compound, a tertiary amine compound, etc. are mentioned.

As a specific example of a benzoin compound, it is benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, for example.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone.

As an example of an anthraquinone compound, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, and 1-chloro anthraquinone are mentioned, for example.

As a specific example of a thioxanthone compound, it is 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, 2, 4- diisopropyl thioxanthone, for example.

Specific examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

As a specific example of a benzophenone compound, for example, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyldiphenyl sulfide, 4-benzoyl -4'-propyldiphenylsulfide.

As a specific example of a tertiary amine compound, For example, an ethanolamine compound, the compound which has a dialkylaminobenzene structure, for example, 4,4'- dimethylamino benzophenone (Nisso Cure MABP by Nippon Soda Co., Ltd.), 4,4 ' -Dialkylaminobenzophenones such as diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (di Dialkylamino group-containing coumarin compounds such as ethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure manufactured by International Bio-Synthetics Co., Ltd.) (Quantacure) DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics Co., Ltd.), isoamylethyl ester of p-dimethylaminobenzoic acid (Kayakyuer DMBI manufactured by Nippon Kayaku Co., Ltd.) , 4-dimethylaminobenzoic acid 2-ethylhexyl (manufactured by Van Dyk) Esolol 507) and 4,4'-diethylaminobenzophenone (EAB by Hodogaya Chemical Co., Ltd.).

Among the above compounds, thioxanthone compounds and tertiary amine compounds are preferable. It is preferable that the thioxanthone compound is contained in the composition of the present invention from the viewpoint of deep hardening, and in particular, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, Thioxanthone compounds, such as 2, 4- diisopropyl thioxanthone, are preferable.

As a compounding quantity of such a thioxanthone compound, Preferably it is 20 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, the ratio of 10 mass parts or less is suitable. When the compounding quantity of a thioxanthone compound is too large, since thick film sclerosis | hardenability will fall and it will lead to the cost increase of a product, it is unpreferable.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As a dialkylamino benzophenone compound, 4,4'- diethylamino benzophenone is preferable at the point of low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has little coloration because the maximum absorption wavelength is in the ultraviolet region, and reflects the color of the colored pigment itself using a color pigment as well as a colorless transparent photosensitive composition. It is possible to provide a colored solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

As a compounding quantity of such a tertiary amine compound, Preferably it is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, it is the ratio of 0.1-10 mass parts. When the compounding quantity of a tertiary amine compound is less than 0.1 mass part, there exists a tendency for sufficient sensitization effect to not be acquired. On the other hand, when it exceeds 20 mass parts, there exists a tendency for the light absorption on the surface of the dry solder resist coating film by a tertiary amine compound to worsen, and deep-curing property falls.

In the photocurable resin composition of the present invention, known conventional N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as the chain transfer agent in order to improve the sensitivity. As a specific example of a chain transfer agent, For example, Chain transfer agent which has carboxyl groups, such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid, and derivatives thereof; Chain transfer agents having hydroxyl groups such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecylmercaptan , Propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanethiol, cyclohexanethiol, thioglycerol, 4,4-thiobisbenzenethiol and the like.

Furthermore, as a heterocyclic compound having a mercapto group functioning as a chain transfer agent, for example, mercapto-4-butyrolactone (alias 2-mercapto-4-butanolide) and 2-mercapto-4-methyl 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy- 2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4-butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto 4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) ethyl-2-mercapto-4-butyrolactam, 2 Mercapto-5-valerolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam , N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam and 2-mercapto-6- Hexanolactam etc. are mentioned.

In particular, as a heterocyclic compound having a mercapto group which is a chain transfer agent which does not impair the developability of the photocurable resin composition, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole , 5-methyl-1,3,4-thiadiazole-2-thiol and 1-phenyl-5-mercapto-1H-tetrazole are preferred. These chain transfer agents can be used individually or in combination of 2 or more types.

These photoinitiators, photoinitiator, and sensitizer can be used individually or as a mixture of 2 or more types.

It is preferable that the total amount of such a photoinitiator, a photoinitiation adjuvant, and a sensitizer is 35 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (A). When it exceeds 35 mass parts, there exists a tendency for deep-part sclerosis | hardenability to fall by these light absorption.

The photopolymerizable monomer (G) used in order to make the composition of this invention into a photocurable resin composition is photocured by active energy ray irradiation, and insolubilizes the photocurable resin composition of this invention in aqueous alkali solution, or is insoluble. It helps to get angry. As such a compound, Diacrylates of glycol, such as ethylene glycol, methoxy tetraethylene glycol, polyethylene glycol, propylene glycol; Polyhydric acrylates such as polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or ethylene oxide adducts or propylene oxide adducts thereof; Polyhydric acrylates, such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether and triglycidyl isocyanurate; And melamine acrylate, and / or each methacrylate corresponding to the acrylate.

Moreover, hydroxyacrylates, such as pentaerythritol triacrylate, and isophorone diisocyanate to the epoxy acrylate resin which made acrylic acid react with polyfunctional epoxy resins, such as a cresol novolak-type epoxy resin, and the hydroxyl group of this epoxy acrylate resin. Epoxy urethane acrylate compounds, etc. which reacted the half urethane compounds of diisocyanate, such as these, are mentioned. Such epoxy acrylate-based resin can improve photocurability without deteriorating the touch dryness.

The compounding quantity of the photopolymerizable monomer (G) which has two or more ethylenically unsaturated groups in such a molecule | numerator is 100 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin (A), More preferably, it is the ratio of 5-70 mass parts. When the said compounding quantity is less than 5 mass parts, since photocurability falls and pattern formation becomes difficult by alkali development after active energy ray irradiation, it is unpreferable. On the other hand, when it exceeds 100 mass parts, since solubility to aqueous alkali solution falls and a coating film becomes weak, it is unpreferable.

Curable resin composition of this invention can mix | blend a coloring agent (H). As a coloring agent (H), conventionally well-known coloring agents, such as red, blue, green, and yellow, can be used, and any of pigments, dyes, and dyes may be used. Specifically, the following color index (C.I .; issued by The Society of Dyers and Colorists) numbers is given. However, it is preferable not to contain a halogen from a viewpoint of reducing environmental load and an influence on a human body.

Red colorant:

Examples of the red colorant include monoazo, disazo, monoazolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone and quinacridone. It can be mentioned.

Monoazo series: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Disazo meter: Pigment Red 37, 38, 41.

Monoazo Lake system: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224 .

Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensation azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

As the blue colorant, there are phthalocyanine-based and anthraquinone-based compounds, and the pigment-based compound is classified as Pigment, specifically: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pig Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

As dye system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 122, solvent blue 136, solvent blue 67, solvent blue 70 may be used. In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:

Examples of the green colorant include phthalocyanine series, anthraquinone series, and perylene series, and specifically, pigment green 7, pigment green 36, solvent green 3, solvent green 5, solvent green 20, solvent green 28, and the like can be used. . In addition to the above, a metal substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone and the like. Specific examples include the following.

Anthraquinone series: solvent yellow 163, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202.

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensation azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo series: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, coloring agents, such as purple, orange, brown, and black, can also be added for the purpose of adjusting a color tone.

Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment There are 23 Brown, CI Pigment Brown 25, CI Pigment Black 1, and CI Pigment Black 7.

Although the mixing | blending ratio of the coloring agent (H) as mentioned above does not have a restriction | limiting in particular, Preferably it is 0-10 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A), Especially preferably, the ratio of 0.1-5 mass parts is sufficient. Do.

The curable resin composition of this invention can mix | blend a filler as needed in order to raise the physical strength of the coating film, etc. As such a filler, known conventional inorganic or organic fillers can be used, but in addition to the above-described aluminum hydroxide and spherical silica, barium sulfate, silica, talc, hydrotalcite, magnesium hydroxide, boehmite, alumina, titanium oxide and the like can be used. These can be combined individually or 2 or more types.

The compounding quantity of these fillers becomes like this. Preferably it is 300 mass parts or less, More preferably, it is 0.1-300 mass parts, Especially preferably, it is 0.1-150 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A). When the compounding quantity of a filler exceeds 300 mass parts, since the viscosity of curable resin composition becomes high and printability falls or hardened | cured material becomes weak, it is unpreferable.

A conventionally well-known binder polymer can be used for curable resin composition of this invention for the purpose of the improvement of flexibility and a touch drying property. As the binder polymer, polymers of cellulose, polyester, and phenoxy resins are preferable. Examples of the cellulose polymers include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) manufactured by Eastman, and by the Toyobo company, Byron series, bisphenol A, bisphenol F, and the like. Phenoxy resins of these hydrogenated compounds are preferred. The addition amount of these binder polymers becomes like this. Preferably it is 50 mass parts or less, More preferably, it is 1-30 mass parts, Especially preferably, it is 5-30 mass parts with respect to 100 mass parts of said carboxyl group-containing resin (A). When the compounding quantity of a binder polymer exceeds 50 mass parts, since alkali developability of curable resin composition falls and developable pot life becomes short, it is unpreferable.

In the curable resin composition of this invention, an adhesion promoter can be used in order to improve the adhesiveness of an interlayer or the adhesiveness of the photosensitive resin layer and a base material. As a specific example, for example, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1 -Phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotria Sol, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent and the like.

In general, since most of the polymer material is oxidatively deteriorated serially once the oxidation starts, and causes a decrease in the function of the polymer material, the curable resin composition of the present invention contains (1) radicals generated in order to prevent oxidation. An antioxidant such as a radical scavenger to invalidate and / or (2) peroxide decomposing agent which decomposes the generated peroxide into a harmless substance and prevents generation of new radicals can be added.

As antioxidant which functions as a radical trapping agent, as a specific compound, hydroquinone, 4-t- butylcatechol, 2-t- butyl hydroquinone, hydroquinone monomethyl ether, 2, 6- di-t- butyl- p-cresol, 2 , 2-methylene-bis (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'-di-t-butyl-4 Phenolic compounds such as -hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6, And amine compounds such as 6-tetramethyl-4-piperidyl) -sebacate and phenothiazine.

Radical scavengers may be commercially available and include, for example, adecastave AO-30, adecastave AO-330, adecastave AO-20, adecastave LA-77, adecastave LA-57, adecas Tab LA-67, Adecastave LA-68, Adecastave LA-87 (above, Asahi Denkasa make, brand name), Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, Ciba Specialty Chemicals make, brand name), etc. are mentioned.

As antioxidant which functions as a peroxide decomposition agent, As a specific compound, Phosphorus type compounds, such as a triphenyl phosphite, a pentaerythritol tetralauryl thio propionate, a dilauryl thiodipropionate, a distearyl 3,3'- thi Sulfur type compounds, such as an odys propionate, etc. are mentioned.

The peroxide decomposer may be commercially available, for example, Adecastab TPP (manufactured by Asahi Denka Corporation, trade name), Mark AO-412S (manufactured by Adeka Agas Chemical Co., Ltd.), smiller TPS (Sumitomo Kaga) Manufactured by Kakusa Co., Ltd., and the like.

Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

In addition, in general, the polymer material absorbs light and thus causes decomposition and deterioration. Thus, in order to take stabilization measures against ultraviolet rays, a ultraviolet absorber can be used for the curable resin composition of the present invention.

Examples of the ultraviolet absorbents include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives. Specific examples of the benzophenone derivatives include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2 And 4-dihydroxy benzophenone. Specific examples of the benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4 -Hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, and the like. Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- ( 2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like Can be mentioned. Specific examples of the triazine derivatives include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine, and the like.

Ultraviolet absorbers may be commercially available and include, for example, tinuvin PS, tinubin 99-2, tinubin 109, tinubin 384-2, tinubin 900, tinubin 928, tinubin 1130, tinubin 400, tinubin 405, tinuvin 460, tinuvin 479 (above, Ciba Specialty Chemicals make, brand name), etc. are mentioned.

Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, It can aim at stabilization of the molding obtained from curable resin composition of this invention by using together with the said antioxidant.

Moreover, the curable resin composition of this invention can use an organic solvent for the synthesis | combination of the said carboxyl group-containing resin (A), adjustment of a composition, or viscosity adjustment for apply | coating to a board | substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum solvents. More specifically, ketones, such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as these; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents are used alone or as a mixture of two or more kinds.

The curable resin composition of the present invention may further contain, if necessary, known conventional thermal polymerization inhibitors, finely divided silicas such as finely divided silica, organic bentonite and montmorillonite, antifoaming agents and / or leveling agents such as silicone, fluorine, and polymers, Known conventional additives such as silane coupling agents such as imidazole series, thiazole series, and triazole series, antioxidants, and rust inhibitors can be blended.

The thermal polymerization inhibitor can be used to prevent thermal polymerization or polymerization over time of the polymerizable compound. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone and 4-methoxy-2-hydroxybenzophenone. Cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl-6-t Butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactants, methyl salicylate and phenothiazine, nitroso compounds, nitroso compounds and chelates of Al Can be mentioned.

Curable resin composition of this invention can also be made into the form of the dry film provided with the carrier film (support) and the layer containing the said curable resin composition formed on the said carrier film.

At the time of dry film formation, the curable resin composition of this invention is diluted with the said organic solvent, it adjusts to an appropriate viscosity, a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater, and a gravure coater. The film can be applied to the carrier film with a spray coater or the like at a uniform thickness and usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about coating film thickness, Generally, the film thickness after drying is suitably selected in 10-150 micrometers, Preferably it is 20-60 micrometers.

A plastic film is used as a carrier film, It is preferable to use plastic films, such as polyester films, such as a polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. Although there is no restriction | limiting in particular about the thickness of a carrier film, Usually, it selects suitably in the range of 10-150 micrometers.

After film formation on the carrier film, it is preferable to further laminate a cover film that can be peeled off the surface of the film for the purpose of preventing dust from adhering to the surface of the film.

As a peelable cover film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, etc. can be used, for example, When peeling a cover film, it is a film | membrane and a cover film rather than the adhesive force of a film | membrane and a carrier film. It is preferable that the adhesive force of is smaller.

Curable resin composition of this invention is adjusted to the viscosity suitable for an application | coating method with the said organic solvent, for example, and it is immersion coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating on a base material. A tack free coating film can be formed by apply | coating by methods, such as a method, and carrying out volatilization (temporary drying) of the organic solvent contained in a composition at the temperature of about 60-100 degreeC. Moreover, in the case of the dry film which apply | coated the said composition on a carrier film, and dried and wound up as a film, after bonding a curable resin composition layer on a base material by a laminator etc. in contact with a base material, a resin film is peeled off by peeling a carrier film. Can be formed.

In the case of the photocurable resin composition, it is then exposed by active energy rays or directly by a laser direct exposure machine through a photomask in which a pattern is formed by a contact type (or non-contact method), and then an unexposed part. Is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution) to form a resist pattern. In the case of the composition containing the thermosetting component (D), for example, by heating to a temperature of about 140 to 180 ° C and thermosetting, the carboxyl group of the carboxyl group-containing resin (A) and two or more cyclic ethers in the molecule A thermosetting component (D) having a group and / or a cyclic thioether group reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, hygroscopicity, adhesiveness, and electrical properties. Moreover, even when it does not contain a thermosetting component (D), by heat-processing, since the ethylenically unsaturated bond which remained in the unreacted state at the time of exposure heat-polymerizes, and a coating film characteristic improves, it heat-processes according to a purpose and a use (heat Curing).

Examples of the substrate include paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven fabric epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine, polyethylene and PPO, in addition to printed wiring boards and flexible printed wiring boards formed in advance. ㆍ Materials such as copper clad laminates for high frequency circuits using cyanate esters are used, and copper clad laminates of all grades (FR-4, etc.), other polyimide films, PET films, glass substrates, ceramic substrates, wafer plates, etc. Can be.

Volatilization drying after apply | coating curable resin composition of this invention is hot-air circulation type drying, and it uses IR, and hotplate in a dryer using a hotplate, a convection oven, etc. (the thing provided with the heat source of the air heating system by steam) And a method of spraying the support from the nozzle).

In the case of a photocurable resin composition, an exposure part (part irradiated with an active energy ray) is hardened by apply | coating and exposing (coating of an active energy ray) with respect to the coating film obtained after volatilizing and drying a solvent.

As an exposure apparatus used for the said active energy ray irradiation, if it is a device which mounts a high pressure mercury lamp lamp, an ultrahigh pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates an ultraviolet-ray in the range of 350-450 nm, a direct drawing apparatus ( For example, a laser direct imaging device which draws an image directly with a laser by CAD data from a computer) can also be used. As the laser light source of the weaving machine, any one of a gas laser and a solid laser may be used as long as the laser light having a maximum wavelength in the range of 350 to 410 nm is used. Although the exposure amount for image formation changes with film thickness etc., it can be generally in the range of 20-800 mJ / cm <2>, Preferably it is 20-600 mJ / cm <2>.

As the developing method, it can be carried out by an immersion method, a shower method, a spray method, a brush method or the like, and an aqueous solution of an alkali such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used. have.

[Example]

Although an Example and a comparative example are shown to the following and this invention is demonstrated concretely, this invention is not limited to the following Example. In addition, below "part" and "%" are mass references | standards unless there is particular notice.

Synthetic example

(A-1) The synthesis | combination of resin corresponding to the said carboxyl group-containing resin (5):

Polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol in a reaction vessel equipped with a stirring device, a thermometer and a condenser (manufactured by Asahi Kasei Chemicals Co., Ltd., TJ5650J, number average molecular weight 800) Was charged with 2400 g (3 mol), 603 g (4.5 mol) of dimethylol propionic acid and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxy compound. Subsequently, 1887 g (8.5 mol) of isophorone diisocyanate was added as a polyisocyanate, and it heated and stopped to 60 degreeC, stirring, heating again when the temperature in a reaction container began to fall, and continued stirring at 80 degreeC, After confirming that the absorption spectrum (2280 cm <^-1> ) of the isocyanate group was lost by the infrared absorption spectrum, reaction was complete | finished. Carbitol acetate was added so that solid content might be 50 mass%. The acid value of solid content of obtained carboxyl group-containing resin was 50 mgKOH / g.

(A-2) Photosensitive carboxyl group-containing resin corresponding to the said carboxyl group-containing resin (7):

Nippon Kayaku Co., Ltd. product ZCR-1601H (solid content 65%; acid value as resin is 98 mgKOH / g) which is a photosensitive carboxyl group-containing resin using the polyfunctional epoxy of biphenyl novolak structure, and having a photosensitive group, A-2 Shall be.

Preparation of aluminum hydroxide slurry:

700 g of aluminum hydroxide (Showy Denko Co., Ltd. Heidilite 42M) and 20 g of carbitol acetate and BYK-110 are mixed and stirred as a solvent, and it disperse | distributes using 0.5 micrometer zirconia beads with a bead mill. It was. This was repeated three times to prepare an aluminum hydroxide slurry (B-1) that was passed through a 3 μm filter.

Preparation of Silica Slurry:

A mixture of 700 g of spherical silica (SO-E2 manufactured by Adma Tech Co., Ltd.), 295 g of carbitol acetate as a solvent, and 5 g of a vinylsilane coupling agent as a silane coupling agent was subjected to dispersion treatment in the same manner as above. . This was repeated three times to prepare a silica slurry (C-1) filtered through a 3 μm filter.

Silica slurry (C-2) was prepared by dispersing 700 g of spherical silica (SO-C5 manufactured by Adma Tech Co., Ltd.) in the same manner as the silica slurry and passing through a 5 μm filter.

Examples 1 to 9 and Comparative Examples 1 to 4

Using the resin solution of the said synthesis example, it mix | blended in the ratio (mass part) shown in Table 1 with the various components shown in Table 1, pre-mixed with a stirrer, and knead | mixed with a triaxial roll mill to manufacture a soldering resist curable resin composition It was. Here, when the dispersion degree of the obtained curable resin composition was evaluated by the particle size measurement by the erycksen company grinder, it was 15 micrometers or less.

Performance rating:

<Optimal exposure amount>

The thermosetting and photocurable resin compositions of Examples 2 to 9 and Comparative Examples 1 to 4 were subjected to buff roll polishing of a circuit pattern substrate having a copper thickness of 35 μm, washed with water, dried, and then applied to the entire surface by screen printing. Dry for 30 minutes in a hot air circulating drying furnace at 80 ° C. After drying, exposure was performed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a metal halide lamp (HMW-680-GW20, manufactured by Oak Seisakusho Co., Ltd.), and developed (90 ° C, 0.2 MPa, 1 wt% Na ₂ CO ₃ solution) to the optimum dose for 6 days when the pattern of the step-tablet which remains when the line for 90 seconds.

Characteristic test:

Solder Heat Resistance

The evaluation board | substrate with which the rosin type flux was apply | coated was immersed in the solder tank previously set to 260 degreeC, and the flux was wash | cleaned with denatured alcohol, and the expansion and peeling of the resist layer by visual observation were evaluated. The criteria are as follows.

(Circle): Peeling is not observed by immersion once for 10 second.

(Triangle | delta): Peeling is not observed by immersion once for 5 second.

X: There exists expansion and peeling in a resist layer once in immersion for 5 second.

<Flammability>

The composition of each Example and the comparative example was apply | coated completely by screen printing to the polyimide film (Kapton 100H, 50H by Toray Dupont) of 12.5 micrometers or 25 micrometers thick, dried at 80 degreeC for 20 minutes, and cooled to room temperature. In addition, the front surface was similarly applied by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature to obtain a double coated substrate. About the board | substrate of Example 1, 60 minutes of thermosetting were performed at 150 degreeC, and it was set as the evaluation sample. About the board | substrate of Examples 2-9 and Comparative Examples 1-4, the soldering resist is fully exposed by the optimal exposure amount using the exposure apparatus (HMW-680-GW20) with a metal halide lamp, and 1 weight% of 30 degreeC The Na ₂ CO ₃ aqueous solution was developed for 90 seconds under a spray pressure of 0.2 MPa, and thermally cured at 150 ° C. for 60 minutes to obtain an evaluation sample. The thin material vertical combustion test based on the UL94 standard was done about this flame retardance evaluation sample. The evaluation is expressed as VTM-0 or NG (which did not achieve VTM-0), based on the UL94 specification.

<Flexibility>

The composition of each Example and the comparative example was apply | coated completely by screen printing to the polyimide film (Kapton 100H of Toray Dupont) of thickness 25micrometer, dried at 80 degreeC for 30 minutes, and cooled to room temperature. About the board | substrate of Example 1, 60 minutes of thermosetting were performed at 150 degreeC, and it was set as the evaluation sample. About the board | substrate of Examples 2-9 and Comparative Examples 1-4, the soldering resist is fully exposed by the optimal exposure amount using the exposure apparatus (HMW-680-GW20) with a metal halide lamp, and 1 weight% of 30 degreeC The Na ₂ CO ₃ aqueous solution was developed for 90 seconds under a spray pressure of 0.2 MPa, and thermally cured at 150 ° C. for 60 minutes to obtain an evaluation sample.

With respect to the obtained evaluation sample, 180 ° bending was repeated several times by bending and bending, and the crack occurrence state in the coverlay at this time was observed with the naked eye and an optical microscope (magnification x 200), and the number of times the crack did not occur was evaluated. It was.

The result of each said evaluation test is put together in Table 2, and is shown.

Examples 10 to 17

The flame-retardant photocurable resin composition prepared by mixing the compositions shown in Examples 2 to 9 in Table 1 without the addition of a silicone antifoaming agent was diluted with methyl ethyl ketone, coated on a carrier film, heated and dried to form a photosensitive resin having a thickness of 20 μm. The composition layer was formed, the cover film was bonded on it, and the dry film was obtained. Then, the cover film was peeled off and the film was bonded to the patterned copper foil board | substrate using a laminator. Using a metal halide lamp is equipped with an exposure apparatus (HMW-680-GW20) in the substrate to expose a solder resist pattern by the optimal exposure amount, and then peeling the carrier film, a 1 wt% Na ₂ CO ₃ aqueous solution for 30 ℃ The development was carried out for 90 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern. Then, heat hardening was performed for 60 minutes in the 150 degreeC hot air dryer, and the test board | substrate was produced. About the test board | substrate which has the obtained hardened film, the evaluation test of each characteristic was done similarly to the above-mentioned test method and evaluation method.

The result of each said evaluation test is put together in Table 3, and is shown.

Claims (11)

Curable resin composition containing (A) carboxyl group-containing resin, (B) aluminum hydroxide, and (C) spherical silica. (D) Curable resin composition of Claim 1 which further contains the thermosetting component which has 2 or more cyclic ether group and / or cyclic thioether group in a molecule | numerator. (E) The phosphorus containing compound is further contained, Curable resin composition of Claim 1 characterized by the above-mentioned. The curable resin composition according to claim 1, further comprising (F) a photopolymerization initiator and (G) a photopolymerizable monomer. The curable resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane structure. The curable resin composition according to claim 1, wherein the carboxyl group-containing resin (A) has a biphenyl novolak structure and an ethylenically unsaturated group. The curable resin composition according to claim 2, wherein the thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups in the molecule is an epoxy resin having a biphenyl novolak skeleton. The curable resin composition according to any one of claims 1 to 7, which is a solder resist. The dry film formed by apply | coating and drying curable resin composition of any one of Claims 1-7 to a film. The dry coating film obtained by laminating on the base material the dry coating film obtained by apply | coating and drying the curable resin composition of any one of Claims 1-7 on a base material, or the dry film formed by apply | coating and drying the said curable resin composition to a film on a base material. Hardened | cured material obtained by thermosetting and / or photocuring. The printed wiring board which has the hardened | cured material of Claim 10.