JP2013033282A - Curable resin composition, and dry film and printed wiring board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that allows formation of a high reflective white coating film layer achieving flame retardancy without using a halogen and having excellent resolution and low warpage property, and to provide a dry film and a cured product of the composition, and a printed wiring board having a flame-retardant film of a solder resist or the like formed thereon by using the composition or the cured product.SOLUTION: The curable resin composition contains at least one in a carboxyl group-containing resin, a novolac epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin and mixtures of these resins, and titanium oxide, and a metal salt of phosphinic acid. In a preferred embodiment, the curable resin composition further contains a thermosetting resin. The carboxyl group-containing resin is preferably a carboxylic acid resin having an urethane skeleton.

Description

  The present invention relates to a flame-retardant curable resin composition, and particularly to a curable resin composition capable of forming a coating film having low warpage and excellent flame retardancy. The present invention also relates to a dry film using such a curable resin composition and a printed wiring board having such a cured coating film.

  Conventionally, printed wiring boards and flexible wiring boards (hereinafter abbreviated as FPC) have been required to be flame retardant because they are mounted on electronic devices, and coating films that are part of these are also required to have flame resistance. Has been. Among these, since the FPC is usually made of a polyimide substrate, it is a thin film unlike a printed wiring board of a glass epoxy substrate. However, since the coating film to be applied has the same film thickness on both the printed wiring board and the FPC, in the case of a thin-film FPC, the burden of flame retardancy on the coating film becomes relatively large.

For this reason, various proposals have conventionally been made for flame retarding of coating films. For example, Japanese Patent Application Laid-Open No. 2007-10794 (Patent Document 1) describes (a) a binder polymer, (b) a halogenated aromatic ring such as a bromophenyl group, and a polymerizable ethylenic group such as a (meth) acryloyl group. Flame retardant for FPC containing a photopolymerizable compound having a saturated bond in the molecule, (c) a photopolymerization initiator, (d) a blocked isocyanate compound, and (e) a phosphorus compound having a phosphorus atom in the molecule. A photosensitive resin composition has been proposed. However, the use of a halogen compound such as a compound having an unsaturated double bond polymerizable with a halogenated aromatic ring is not preferable from the viewpoint of environmental load.
On the other hand, FPCs equipped with light emitting diodes (LEDs) have demands for high reflectivity, bending resistance, and resolution. However, if a high reflectivity is pursued, a solder resist that sufficiently satisfies the requirements cannot be obtained, for example, bending resistance and resolution are lowered.

JP 2007-10794 A (Claims)

The present invention has been made to solve the above-described problems of the prior art, and its main purpose is to achieve halogen-free flame retardancy and to achieve high resolution and low warpage. It is providing the curable resin composition which can form a reflective white coating film layer.
Furthermore, an object of the present invention is to provide a dry film and a cured coating film having low warpage and excellent flame retardancy, and a printed wiring having a flame retardant coating film having such excellent characteristics by using such a curable resin composition. To provide a board.

To achieve the above object, according to the present invention, at least one of a carboxyl group-containing resin, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin and a mixture thereof, titanium oxide And a phosphinic acid metal salt. A curable resin composition is provided.
According to this invention, the curable resin composition characterized by including a thermosetting resin further is provided.
In addition, according to the present invention, there is provided a curable resin composition wherein the carboxyl group-containing resin is a carboxylic acid resin having a urethane skeleton.

Moreover, according to this invention, the dry film formed by apply | coating and drying the said curable resin composition to a film is provided.
Furthermore, according to this invention, the cured coating film obtained by heat-curing or photocuring or photocuring and heat-curing the dry film formed by apply | coating and drying the said curable resin composition or the said curable resin composition to a film. Is provided.

  Furthermore, according to the present invention, the curable resin composition or the dry film obtained by applying and drying the curable resin composition on a film is cured by heat curing or photocuring or photocuring and thermosetting. A printed wiring board having a coating is also provided.

According to the curable resin composition of the present invention, a carboxyl group-containing resin, a novolac-type epoxy resin, a heterocyclic epoxy resin, a bisphenol A-type epoxy resin, and a mixture thereof, at least one epoxy resin, titanium oxide, and Since it contains a phosphinic acid metal salt, it can form a coating film having a non-halogen composition, low environmental burden, excellent flame retardancy, and excellent resolution and low warpage.
Moreover, since the coating film formed here contains titanium oxide which is a white pigment, it has a high whiteness and is highly reflective and useful for backlights of liquid crystal panels.

As a result of diligent research to achieve the above-described problems, the present inventors have found that at least one epoxy selected from a carboxyl group-containing resin, a novolac epoxy resin, a heterocyclic epoxy resin, a bisphenol A epoxy resin, and a mixture thereof. The curable resin composition containing a resin, titanium oxide, and phosphinic acid metal salt has not only high whiteness and high reflectance, but also good resolution can be obtained by improving development resistance. I found it. The fact that such an effect can be obtained by using the combination of the three components is a surprising effect that is not expected from the prior art.
Hereinafter, each component of the curable resin composition of the present invention will be described in detail.

  As the carboxyl group-containing resin, conventionally known various carboxyl group-containing resins having a carboxyl group in the molecule for the purpose of imparting a crosslinking reaction, adhesion and alkali developability can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and development resistance as a photosensitive composition for performing alkali development. And the unsaturated double bond is preferably derived from acrylic acid, methacrylic acid or derivatives thereof. In addition, when using only the carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, the photosensitivity having a plurality of ethylenically unsaturated groups in the molecule described later. It is necessary to use a compound (photopolymerizable monomer) in combination.

As specific examples of the carboxyl group-containing resin, the following compounds (any of oligomers and polymers) are preferable.
(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-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, polycarbonate polyols, and polyethers Diol compounds such as polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups, and optionally one alcoholic hydroxyl group A carboxyl group-containing urethane resin obtained by a polyaddition reaction with a compound having an acid.

  (3) Diisocyanate and bifunctional epoxy resin such as 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, biphenol type epoxy resin ( A carboxyl group-containing photosensitive urethane resin obtained by a polyaddition reaction of (meth) acrylate or a partially acid anhydride-modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

  (4) During the synthesis of the resin of (2) or (3), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing photosensitive urethane resin.

  (5) During the synthesis of the resin of (2) or (3), one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing photosensitive urethane resin obtained by adding a compound having a terminal (meth) acrylate.

  (6) Carboxyl group-containing photosensitivity in which (meth) acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin as described later and a dibasic acid anhydride is added to the hydroxyl group present in the side chain. Resin.

  (7) A polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin is reacted with (meth) acrylic acid, and a dibasic acid anhydride is added to the resulting hydroxyl group. Added carboxyl group-containing photosensitive resin.

  (8) A dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid is reacted with a bifunctional oxetane resin as described later, and the resulting primary hydroxyl group is phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. A carboxyl group-containing polyester resin to which a dibasic acid anhydride such as

  (9) Bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, etc. The reaction product obtained by reacting a compound having a reactive hydroxyl group with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid, and the resulting reaction product is reacted with a polybasic acid anhydride. A carboxyl group-containing photosensitive resin obtained by causing the reaction to occur.

  (10) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

  (11) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.

  (12) In addition to the resins (1) to (11) above, one epoxy group and one or more (meth) acryloyl groups in one molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate A carboxyl group-containing photosensitive resin obtained by adding a compound having the following.

  In addition, in this specification, (meth) acrylate is a term that collectively refers to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin is desirably in the range of 20 to 120 mgKOH / g, and more preferably in the range of 40 to 100 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 20 mgKOH / g, the adhesion of the coating film cannot be obtained, or alkali development becomes difficult in the case of the photocurable resin composition.
On the other hand, when the acid value exceeds 120 mgKOH / g, the warp of the cured coating film becomes very large, and it is not suitable as the intended coating agent for FPC. Further, in the case of a photocurable resin composition, it is not preferable because it is dissolved and peeled off with a developer without distinction between an exposed portion and an unexposed portion, and it becomes difficult to draw a normal resist pattern. Preferred carboxyl group-containing resins are those having an acid value of 20 to 60 mg KOH / g in the case of a thermosetting resin composition.
It is preferable from the viewpoint of adhesion and low warpage, and when imparting developability, it is preferable to use a resin having an acid value of 60 to 120 mgKOH / g in combination with these resins.

As the low acid value resin, a urethane group-containing carboxyl group-containing polyurethane is preferable from the viewpoint of adhesion and low warpage, and as the high acid value resin, it is difficult to be a carboxyl group-containing resin having an aromatic ring. It is preferable from the viewpoints of flame retardancy, heat resistance, and developability.
If this relationship is reversed, in the case of a photocurable resin composition that requires development, poor development occurs, resulting in poor low warpage and bendability.
Particularly preferred urethane resins are those using polyester polyol, polycarbonate diol, polyether and aliphatic and alicyclic isocyanates as raw materials. Moreover, as a carboxyl group-containing resin having an aromatic ring, a resin having a biphenyl novolac structure is preferable from the viewpoint of flame retardancy and heat resistance.

  Furthermore, in the carboxyl group-containing photosensitive resin synthesized from a compound having a phenolic hydroxyl group such as (9) and (10), a photoreactive group and a thermosetting reactive group exist independently. It is preferable because it has little curing shrinkage and is excellent in low warpage and folding resistance.

  Moreover, although the weight average molecular weight of the said carboxyl group containing resin changes with resin frame | skeletons, what is generally in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. If the weight average molecular weight is less than 2,000, the tack-free performance of the coating film may be inferior, the moisture resistance of the coating film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated, and the storage stability of the composition may be inferior.

The amount of such a carboxyl group-containing resin is 20 to 60% by mass, preferably 30 to 50% by mass in the entire composition. When the amount of the carboxyl group-containing resin is less than the above range, the film strength is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition is increased or the coating property is lowered, which is not preferable.
These carboxyl group-containing resins can be used without being limited to those listed above, and can be used by mixing one kind or plural kinds.

  As the titanium oxide used in the curable resin composition of the present invention, a sulfuric acid method, a chlorine method, a rutile type, anatase type, a surface treatment with a hydrated metal oxide, or a surface treatment with an organic compound was performed. Titanium oxide or the like can be used. Among these titanium oxides, rutile type titanium oxide is more preferable. Anatase-type titanium oxide is often used because of its high whiteness compared to the rutile type. However, since anatase-type titanium oxide has photocatalytic activity, it may cause discoloration of the resin in the photocurable resin composition. On the other hand, rutile titanium oxide has a slightly lower whiteness than the anatase type, but has almost no photoactivity, so that a stable coating film can be obtained.

  As a rutile type titanium oxide, a well-known rutile type thing can be used. Specifically, TR-600, TR-700, TR-750, TR-840 manufactured by Fuji Titanium Industry Co., Ltd., R-550, R-580, R-630, R-820 manufactured by Ishihara Sangyo Co., Ltd., CR-50, CR-60, CR-90, CR-97, KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd. can be used. Among these rutile titanium oxides, it is particularly preferable to use titanium oxide whose surface is treated with hydrous alumina or aluminum hydroxide from the viewpoints of dispersibility, storage stability, and flame retardancy.

  The compounding quantity of such a titanium oxide is 1-500 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, Preferably it is 5-300 mass parts. When the blending amount is less than 1 part by mass, the low warpage property and flame retardancy of the cured coating film cannot be obtained sufficiently, which is not preferable. On the other hand, when the amount exceeds 500 parts by mass, it is difficult to obtain sufficient flexibility of the cured coating film, which is not preferable.

（式（Ｉ）中、Ｒ^１、Ｒ^２は、それぞれ、炭素数１〜６のアルキル基又は炭素数１２以下のアリール基を表し、Ｍは、カルシウム、アルミニウム又は亜鉛を表し、Ｍ＝アルミニウムのときｍ＝３であり、それ以外の金属のときはｍ＝２である。） The curable resin composition of the present invention is characterized by containing a phosphinic acid metal salt. By using a phosphinic acid metal salt, both the flexibility and flame retardancy of the cured coating film can be achieved. Moreover, since the phosphinic acid metal salt is not dissolved in the coating film but is dispersed, good resolution can be obtained. As the phosphinic acid metal salt, a compound represented by the following general formula (I) can be preferably used.

(In the formula (I), R ¹ and R ² each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms, M represents calcium, aluminum or zinc, and M = aluminum. (When m = 3, m = 2 when other metals are used.)

Moreover, by using a phosphinic acid metal salt having excellent heat resistance, it is possible to suppress the bleed-out of the flame retardant in the hot press during mounting.
Examples of commercially available phosphinic acid metal salts include Clariant's EXOLIT OP 1230, EXOLIT OP 930, and EXOLIT OP 935.

  The blending amount of these phosphinic acid metal salts is desirably in the range of 1 to 100 parts by weight, preferably 3 to 80 parts by weight, and more preferably 5 to 70 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin. .

  When the resin composition of the present invention is composed into a thermosetting resin composition or a photocurable thermosetting resin composition, the properties such as heat resistance and insulation reliability of the cured coating film are improved. For this purpose, at least one epoxy resin among novolac type epoxy resin, heterocyclic epoxy resin, bisphenol A type epoxy resin and mixtures thereof is blended. Moreover, the conventionally well-known thermosetting component which can react with the carboxyl group which the said carboxyl group-containing resin has can be mix | blended.

  A preferred thermosetting component for the curable resin composition of the present invention is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as “cyclic (thio) ether groups”) in the molecule. It is. Among them, a bifunctional epoxy resin is preferable, and diisocyanate and its bifunctional blocked isocyanate can also be used.

  Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a plurality of thioether groups in the molecule The compound which has this, ie, an episulfide resin etc. are mentioned.

  As the polyfunctional epoxy compound, for example, jER828, jER834, jER1001, jER1004 manufactured by Japan Epoxy Resin, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011 manufactured by Tohto Kasei Co., Ltd. YD-013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Ciba Japan's Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Kogyo A . E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Japan Epoxy Resin, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., Dow Chemical Company D. E. R. 542, Araldide 8011 manufactured by Ciba Japan, Sumi-epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. E. R. 711, A.I. E. R. 714 (both trade names) brominated epoxy resin; jER152, jER154 manufactured by Japan Epoxy Resin, D.C. E. N. 431, D.D. E. N. 438, Epicron N-730 manufactured by DIC, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., Araldide ECN1235, Araldide ECN1273, Araldide ECN1299 manufactured by Ciba Japan Araldide XPY307, manufactured by Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000L, NC-3000, NC-3000H, NC-3100, manufactured by Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220, A.A. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175 manufactured by Toto Kasei Co., YDF- 2004, bisphenol F type epoxy resin such as Araldide XPY306 manufactured by Ciba Japan Co., Ltd. (all trade names); hydrogenated bisphenol such as Epototo ST-2004, ST-2007, ST-3000 (trade names) manufactured by Tohto Kasei Type A epoxy resin: jER604 manufactured by Japan Epoxy Resin, Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Japan, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. ) Glycidylamine type epoxy resin; Hydantoin type epoxy resins such as Araldide CY-350 (trade name) manufactured by Bread; Celoxide 2021 manufactured by Daicel Chemical Industries, and alicyclic epoxy such as Araldide CY175 and CY179 manufactured by Ciba Japan Resin; YL-933 manufactured by Japan Epoxy Resin Co., Ltd. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd .; Bisphenol A novolak type epoxy resin such as epoxy resin jER157S (trade name); Tetraphenylolethane type such as jERYL-931 from Japan Epoxy Resin, Araldide 163 from Ciba Japan Co., Ltd. (all trade names) Epoxy resin; Aral made by Ciba Japan Id PT810, a heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries (all trade names); a diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; a tetraglycidyl xyleno such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. Irethane resin; Nippon Steel Chemical Co., Ltd. ESN-190, ESN-360, DIC Corporation HP-4032, EXA-4750, EXA-4700 and other naphthalene group-containing epoxy resins; DIC Corporation HP-7200, HP-7200H Epoxy resins having a dicyclopentadiene skeleton such as CP-50S and CP-50M glycidyl methacrylate copolymer epoxy resins manufactured by Nippon Oil &Fats; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene Rubber derivatives (eg Iseru Chemical Co. PB-3600, etc.), CTBN modified epoxy resin (e.g., Tohto Kasei Co. YR-102, YR-450, etc.) and others as mentioned, is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these epoxy resins, novolak-type epoxy resins, heterocyclic epoxy resins, bisphenol A-type epoxy resins or mixtures thereof are particularly preferable, and more preferable epoxy resins are epoxy resins having a biphenyl novolak skeleton, particularly heat resistance. Flame retardancy can be improved. As a commercial item, Nippon Kayaku Co., Ltd. NC-3000L, NC-3000, NC-3000H, NC-3100 etc. are mentioned.

  Examples of the polyfunctional oxetane compound 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) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Japan Epoxy Resins. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The amount of the thermosetting component such as a compound having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.3 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. More preferably, it is in the range of 0.5 to 2.0 equivalents. When the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is less than 0.3, the crosslinking reaction with the carboxyl group-containing resin is reduced, so that heat resistance, alkali resistance, electricity This is not preferable because the insulating property is lowered. On the other hand, when the amount exceeds 2.5 equivalents, the low molecular weight cyclic (thio) ether group remains in the dry coating film, which is not preferable because the strength of the coating film decreases.

  When using a thermosetting component such as a compound having a plurality of cyclic (thio) ether groups in the molecule, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; phosphorus compounds such as triphenylphosphine, and those that are commercially available ,example 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., U-CAT (registered trademark) 3503N, U-CAT3502T (both dimethyl) Trade names of blocked isocyanate compounds of amines), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient at a normal quantitative ratio. For example, the thermosetting catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts per 100 parts by mass of the carboxyl group-containing resin. 0.0 part by mass.

  In order to improve the curability of the composition and the toughness of the resulting cured film, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be added to the curable resin composition of the present invention. . Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are 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- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used.
Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. 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 compounds exemplified above.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, 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, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (trade name, manufactured by Asahi Kasei Chemicals Corp.) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.

  The compounding amount of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is less than 50 parts by mass, more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. The ratio is appropriate. When the blending amount exceeds 50 parts by mass, storage stability is lowered, which is not preferable. Particularly preferred is the combined use with an epoxy resin having a biphenyl novolak skeleton, and the blending amount at that time is 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin.

（式中、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、ハロゲン原子以外の置換基を示す。） The curable resin composition of the present invention may be used in combination with a phosphorus compound other than the phosphinic acid metal salt for the purpose of further improving the flame retardancy. As the phosphorus compound other than the phosphinic acid metal salt, those conventionally known as organophosphorus flame retardants can be used. Phosphate esters and condensed phosphate esters, cyclic phosphazene compounds, phosphazene oligomers, or the following general formula ( There is a compound represented by II).

(In formula, R < ³ >, R < ⁴ > and R < ⁵ > show substituents other than a halogen atom each independently.)

  Commercially available products of the compound represented by the above general formula (II) include HCA, SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sanko Co., Ltd.) and the like.

  Examples of phosphorus compounds other than the particularly preferred phosphinic acid metal salts used in the present invention include (1) those having an acrylate group as a reactive group, (2) those having a phenolic hydroxyl group, (3) oligomers or polymers, and (4) Phenoxyphosphazene oligomer is mentioned.

(1) Phosphorus compound having an acrylate group Phosphorus element-containing acrylate has a phosphorus element and is preferably a compound containing a plurality of (meth) acrylates in the molecule. Specifically, in the general formula (II) Examples thereof include compounds in which R ³ and R ⁴ are hydrogen atoms and R ⁵ is an acrylate derivative. Generally, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and known conventional compounds are used. It can be synthesized by a Michael addition reaction with a polyfunctional acrylate monomer.

  Examples of the known and commonly used acrylate monomers include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate. Polyhydric alcohols such as polyhydric acrylates such as these adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide additions of these phenols Polyhydric acrylates such as products; and urethane acrylates of the above polyalcohols, glycerin Diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

(2) Phosphorus compound having a phenolic hydroxyl group The phosphorus compound having a phenolic hydroxyl group is highly hydrophobic and heat resistant, has no deterioration in electrical properties due to hydrolysis, and has high solder heat resistance. Also, as a suitable combination, by using an epoxy resin having a biphenyl skeleton or other epoxy resin as a thermosetting component, it reacts with the epoxy resin and is taken into the network, so that it does not bleed out after curing. Benefits are gained. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.

(3) Oligomers or Polymers Phosphorus compounds that are oligomers or polymers have the advantage that there is little decrease in bendability due to the influence of the alkyl chain, and there is no bleeding out after curing because of the large molecular weight. Commercially available products include Sanko Co., Ltd. M-Ester-HP, Toyobo Co., Ltd. Byron 337, and the like.

(4) Phosphazene oligomer As the phosphazene oligomer, a phenoxyphosphazene compound is effective, and there is a substituted or unsubstituted phenoxyphosphazene oligomer or a trimer, tetramer, pentamer cyclic product, There are liquid and solid powders, both of which can be suitably used. Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd.

  These phosphorus compounds other than the phosphinic acid metal salts can be used singly or in combination.

  The amount of the phosphorus compound other than the phosphinic acid metal salt is suitably 150 parts by mass or less, particularly preferably 100 parts by mass or less, relative to 100 parts by mass of the carboxyl group-containing resin. When the compounding amount of the phosphorus compound other than the phosphinic acid metal salt exceeds 150 parts by mass, the bleedout of the flame retardant and the bending characteristics of the cured coating film are deteriorated, which is not preferable.

  Among the phosphorus compounds other than the above-mentioned phosphinic acid metal salts, preferred are those having a reactive group, a phosphorus element-containing polymer, and a phosphazene oligomer. An element-containing acrylate compound is preferable from the viewpoint of bleeding out, and a phosphorus element-containing polyester polymer is preferable from the viewpoint of adhesion. As the phosphazene oligomer, phenoxyphosphazene is preferable from the viewpoint of heat resistance, and further substituted phenoxyphosphazene having a substituent such as a cyano group or an alkyl group is preferable from the viewpoint of solubility.

  Aluminum hydroxide can be added to the curable resin composition of the present invention. The purpose of using aluminum hydroxide is not only to improve flame retardancy, but especially when it is made into a photocurable resin composition, the affinity and refractive index are close to that of a photosensitive resin, so that photocuring is efficient. In the point of progress

  The aluminum hydroxide used for this invention can use a general purpose well-known thing. Commercially available products include Showa Denko's Heidilite series, HW, H21, H31, H32, H42M, H43M, and the like. In addition, since the one where the particle size of aluminum hydroxide is fine is more effective for bending resistance, it is dispersed in advance to the primary particle size with a bead mill or the like together with a solvent or resin, and filtered to 3 μm or more, more preferably 1 μm. It is preferable to filter and select the above from the viewpoint of flame retardancy and bendability of the resulting cured film.

  The compounding quantity of such aluminum hydroxide is 300 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin, Preferably it is 200 mass parts or less. When the amount exceeds 300 parts by mass, the bendability is deteriorated, which is not preferable.

  When the resin composition of the present invention is formed into a photocurable resin composition or a photocurable thermosetting resin composition, a photopolymerization initiator can be blended. Preferred initiators include one or more photopolymerization selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and an acylphosphine oxide photopolymerization initiator. Initiators can be used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０か１の整数である。） Examples of commercially available oxime ester photopolymerization initiators include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by Ciba Japan, and N-1919, NCI-831 manufactured by Adeka. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

(In the formula, X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms). A group, an amino group, an alkylamino group having an alkyl 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), And Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number 1). Alkyl group having 1 to 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) 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, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or Represents an anthryl group, a pyridyl group, a benzofuryl group, a benzothienyl group, and Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene , Anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1.)

  In particular, in the above general formula, X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable.

  It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of said carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photocurability is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when the amount exceeds 5 parts by mass, light absorption on the surface of the coating film becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5-3 mass parts.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by Ciba Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Commercially available products include Lucilin TPO manufactured by BASF, Irgacure 819 manufactured by Ciba Japan.

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. If it is less than 0.01 parts by mass, the photo-curability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance deteriorate. On the other hand, when the amount exceeds 15 parts by mass, the effect of reducing the outgas cannot be obtained, the light absorption on the surface of the coating film becomes intense, and the deep curability tends to decrease. More preferably, it is 0.5-10 mass parts.

  Other photopolymerization initiators, photoinitiator assistants and sensitizers that can be suitably used in the curable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenone compounds. A tertiary amine compound, a xanthone compound, etc. can be mentioned.

  Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.

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

  Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like.

  Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

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

  Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4, Dialkylaminobenzophenone such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Bio-Synthetics), 4-dimethylamino Nobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol 507 manufactured by Van Dyk), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of said carboxyl group-containing resin. When the blending amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability is lowered and the cost of the product is increased. More preferably, it is 10 parts by mass or less.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.

  As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored, and use colored pigments as well as colorless and transparent photosensitive compositions, and colors that reflect the color of the colored pigments themselves A membrane can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable.

  As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of said carboxyl group-containing resin. When the compounding amount of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect tends not to be obtained. If it exceeds 20 parts by mass, the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts.

These photopolymerization initiators, photoinitiator assistants, and sensitizers can be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as needed to enhance surface photoreactivity, and changes the line shape and opening of the coating to vertical, tapered, or inversely tapered, as well as processing the line width and opening diameter Accuracy can be improved.

  Among the above-mentioned photopolymerization initiators, acylphosphine oxide-based initiators are particularly preferable, and have the best light transmittance from the photobleaching performance, and have a phosphorus element to efficiently promote radical polymerization. In addition, it has been found that the growth terminal is effective as a flame retardant imparting material because it has a structure containing phosphorus element. Further, the oxime ester-based initiator has good initiator efficiency and is effective for improving sensitivity in a small amount. Therefore, the volume change due to outgassing during heat treatment after resist film formation is small, and it is effective in reducing the warpage of the film, which is preferable. . Particularly preferred is a combination of both.

  The photosensitive compound having a plurality of ethylenically unsaturated groups in the molecule used when the curable resin composition of the present invention is photocurable is photocured by irradiation with active energy rays and contains the carboxyl group. The resin is insolubilized in an alkaline aqueous solution, or helps insolubilization. As such a photosensitive compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate can be used, specifically, Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide Acrylamides such as N, N-dimethylaminopropyl acrylamide; N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl Aminoalkyl acrylates such as acrylates; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone Polyvalent acrylates such as adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, tri Multivalent acrylate of glycidyl ethers such as methylolpropane triglycidyl ether and triglycidyl isocyanurate Not limited to the above, but also acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates, and / or the above acrylates And methacrylates corresponding to the above.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  The compounding quantity of the photosensitive compound which has several ethylenically unsaturated groups in such a molecule | numerator is 5-100 mass parts with respect to 100 mass parts of said carboxyl group-containing resin, More preferably, it is 10-70 mass parts. Is the ratio. When the blending amount is less than 5 parts by mass, photocurability is lowered, and pattern formation becomes difficult by alkali development after irradiation with active energy rays, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the coating film becomes brittle. Particularly preferred among these are polyfunctional acrylates such as pentaerythritol, dipentaerythritol, trimethylolpropane and other polyols that are molecularly extended with ethylene oxide, propylene oxide, and caprolactone, and bifunctional polyethers, polyesters, and polycarbonates. The urethane acrylate is preferred.

  The curable resin composition of the present invention can contain a colorant. As the colorant, conventionally known colorants such as red, blue, green and yellow can be used, and any of pigments, dyes and dyes may be used. Specific examples include those with the following color index numbers (CI: issued by The Society of Dyer's and Colorists). However, it is preferable not to contain a halogen from the viewpoint of reducing the environmental burden and affecting the human body.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. It is done.
Monoazo: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 15, 16, 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 type: 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: 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 24, Pigment Red 24,
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, and 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:
Blue colorants include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds are classified as Pigment, specifically: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue. 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, and Pigment Blue 60.
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 97, SolBlu 97, SolBlu 97, SolBlu 97, SolBlu 97 Blue 70 or the like can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, the green colorant includes phthalocyanine, anthraquinone, and perylene. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like.
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.
Condensed azo type: 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 type: 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: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, a colorant such as purple, orange, brown, or black may be added for the purpose of adjusting the color tone.
Specifically, Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, C.I. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73, C.I. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment black 1, C.I. I. Pigment Black 7 etc.

  The mixing ratio of the colorant as described above is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. It is.

  The curable resin composition of the present invention can contain a filler as necessary in order to increase the physical strength of the coating film. As such a filler, publicly known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica, hydrotalcite and talc are preferably used. Further, metal hydroxides such as metal oxides and magnesium hydroxide can be used as extender pigment fillers.

  The amount of these fillers is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. . When the blending amount of the filler exceeds 500 parts by mass, the viscosity of the curable resin composition becomes high and the printability is lowered, or the cured product becomes brittle.

  Furthermore, the curable resin composition of the present invention can use an organic solvent for the synthesis of the carboxyl group-containing resin, the preparation of the composition, or the viscosity adjustment for application to a substrate or a carrier film. .

  Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. 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 Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such organic solvents are used alone or as a mixture of two or more.

  In the curable resin composition of the present invention, in order to prevent oxidation, a radical scavenger that invalidates the generated radical and / or the generated peroxide is decomposed into a harmless substance and no new radical is generated. An antioxidant such as a peroxide decomposer can be added.

  Specific examples of the antioxidant include hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2 -Methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-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-hydroxybenzyl)- Phenolic compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetramethyl-4-pipe Jill) - sebacate, and the like amine compounds such as phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by Asahi Denka Co., Ltd., trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN HI Japan 100 Product name).

  Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

The peroxide decomposing agent may be a commercially available one. For example, ADK STAB TPP (trade name, manufactured by Asahi Denka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), Smizer And TPS (trade name, manufactured by Sumitomo Chemical Co., Ltd.).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

  In the curable resin composition of the present invention, an ultraviolet absorber can be used in addition to the above-mentioned antioxidant in order to take a countermeasure against stabilization against ultraviolet rays.

  Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone. Is mentioned. Specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t. -Butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. Specific examples of the benzotriazole derivative include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like. Specific examples of the triazine derivative include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

  Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by Ciba Japan, trade name) and the like.

  Said ultraviolet absorber can be used individually by 1 type or in combination of 2 or more types, By using together with the said antioxidant, stabilization of the cured film obtained from the curable resin composition of this invention is possible. I can plan.

  When the resin composition of the present invention is composed as a photocurable resin composition or a photocurable thermosetting resin composition, N phenylglycines known and commonly used as chain transfer agents in order to improve sensitivity, Phenoxyacetic acid, thiophenoxyacetic acid, mercaptothiazole and the like can be used. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group, such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2, 2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  A polyfunctional mercaptan-based compound can be used and is not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide. Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythrito Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohols such as erythritol tetrakis (3-mercaptopropionate) and dipentaerythritol hexakis (3-mercaptopropionate) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 ( Poly (mercaptobutyrate) s such as 1H, 3H, 5H) -trione and pentaerythritol tetrakis (3-mertapbutyrate) can be used.

  Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (manufactured by Showa Denko KK).

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 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-va Lolactone, 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, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2 , 4,6-trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: merchandise) Name Disnet DB), and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disne) Door AF), and the like.

  In particular, as a heterocyclic compound having a mercapto group which is a chain transfer agent that does not impair the developability of the photocurable resin composition or the photocurable thermosetting 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 alone or in combination of two or more.

  In the curable resin composition of the present invention, an adhesion promoter can be used in order to improve adhesion between layers or adhesion between a coating layer and a substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Axel M manufactured by Kawaguchi Chemical Industry Co., Ltd.). 3-morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazol-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzo Examples include triazole, amino group-containing benzotriazole, and silane coupling agent.

  The curable resin composition of the present invention may further include, as necessary, known and commonly used thermal polymerization inhibitors, known and commonly used thickeners such as finely divided silica, organic bentonite, and montmorillonite, silicones, fluorines, and polymers. Conventional additives such as an antifoaming agent and / or a leveling agent, silane coupling agents such as imidazole, thiazole, and triazole, antioxidants, rust inhibitors, and the like can be blended.

  The thermal polymerization inhibitor can be used for preventing thermal polymerization or polymerization with 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, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method with the organic solvent, for example, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Moreover, a resin insulation layer can be formed by apply | coating the said composition on a carrier film, and drying and winding up as a film together on a base material. Then, in the case of a photocurable resin composition or a photocurable thermosetting resin composition, the entire surface may be exposed with a conveyor type photocuring apparatus that irradiates active energy rays. Further, the contact pattern or the non-contact pattern is selectively exposed through an active energy ray through a photomask having a pattern formed thereon or directly exposed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (eg, 0.3 to 3 wt. The resist pattern is formed by development with a sodium carbonate aqueous solution. Furthermore, in the case of a thermosetting resin composition or a photocurable thermosetting resin composition, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin and molecules A cured coating film that has excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties due to the reaction of thermosetting components having multiple cyclic ether groups and / or cyclic thioether groups. Can be formed. Even in the case of a photocurable resin composition that does not contain a thermosetting component, the heat treatment causes heat-free radical polymerization of the ethylenically unsaturated bond of the photocurable component remaining in an unreacted state during exposure. In order to improve the coating properties, heat treatment (thermosetting) may be performed depending on the purpose and application.

  Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) using other materials such as epoxy, fluorine, polyethylene, PPO, cyanate ester, etc., and other polyimide films, PET films Glass substrate, ceramic substrate, wafer plate and the like.

  Volatile drying performed after the application of the curable resin composition of the present invention is performed by using a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven, or the like (with a steam-heated air source). Can be carried out by using a counter-current contact method and a method of spraying a nozzle on a support.

  After applying the curable resin composition of the present invention as described above and evaporating and drying the solvent, the obtained coating film is exposed (irradiated with active energy rays). In the coating film, the exposed portion (the portion irradiated by the active energy ray) is cured.

The exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc. A direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used.
The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 2000 mJ / cm ² , preferably 20 to 1500 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method or the like, and as a developer, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  The curable resin composition of the present invention is a dry film having a coating layer formed by applying and drying a curable resin composition on a film of polyethylene terephthalate or the like in advance, in addition to a method of directly applying to a substrate in a liquid state. It can also be used in the form. The case where the curable resin composition of this invention is used as a dry film is shown below.

  The dry film has a structure in which a carrier film, a coating layer, and a peelable cover film used as necessary are laminated in this order. The coating layer is a layer obtained by applying and drying the curable resin composition on a carrier film or a cover film. After forming the coating film layer on the carrier film, a dry film can be obtained by laminating the cover film thereon or forming the coating film layer on the cover film and laminating this laminate on the carrier film.

  As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.

  The coating layer is formed by uniformly applying a curable resin composition to a carrier film or a cover film with a thickness of 10 to 150 μm using a blade coater, a lip coater, a comma coater, a film coater or the like, and then drying.

  As the cover film, a polyethylene film, a polypropylene film, or the like can be used, but it is preferable that the adhesive force with the coating layer is smaller than that of the carrier film.

  To produce a protective film (permanent protective film) on a printed wiring board using a dry film, peel off the cover film, overlay the coating layer and the substrate on which the circuit is formed, and bond them together using a laminator, etc. A coating layer is formed on the formed substrate. If the formed coating layer is exposed, developed, and heat-cured in the same manner as described above, a cured coating layer can be formed. The carrier film may be peeled off either before exposure or after exposure.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Synthesis example 1
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having a plurality of alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer, and a condenser (T5650J manufactured by Asahi Kasei Chemicals Corporation) , 3600 g (4.5 mol) of number average molecular weight 800), 814 g (5.5 mol) of dimethylol butanoic acid, and 118 g (1.6 mol) of n-butanol as a molecular weight regulator (reaction terminator). did. Next, 2009 g (10.8 mol) of trimethylhexamethylene diisocyanate was added as an isocyanate compound having no aromatic ring, and the mixture was heated to 60 ° C. with stirring and stopped, and when the temperature in the reaction vessel began to decrease. It heated again and stirring was continued at 80 degreeC, it confirmed that the absorption spectrum (2280cm < ^-1 >) of the isocyanate group disappeared in the infrared absorption spectrum, and reaction was complete | finished. Subsequently, carbitol acetate was added so that a solid content might be 60 wt%, and the viscous liquid carboxyl group-containing resin containing a diluent was obtained. The acid value of the solid content of the obtained carboxyl group-containing polyurethane was 49.8 mgKOH / g. Hereinafter, the resin solution of this reaction product is referred to as Varnish A-1.

Synthesis example 2
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 2400 g of polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (manufactured by Asahi Kasei Chemicals Corporation, T5650J, number average molecular weight 800) (3 mol), 603 g (4.5 mol) of dimethylolpropionic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound were added. Next, 1887 g (8.5 mol) of isophorone diisocyanate was added as a polyisocyanate, and the mixture was stopped by heating to 60 ° C. while stirring. When the temperature in the reaction vessel began to decrease, the mixture was heated again and stirred at 80 ° C. The reaction was terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) had disappeared in the infrared absorption spectrum. Carbitol acetate was added so that the solid content was 50% by mass. The acid value of the solid content of the obtained carboxyl group-containing resin was 50 mgKOH / g. Hereinafter, the resin solution of this reaction product is referred to as Varnish A-2.

Synthesis example 3
In a separable flask, as a bisphenol A type epoxy compound, 368.0 g of RE310S (bifunctional bisphenol A type epoxy resin, epoxy equivalent: 184 g / equivalent) manufactured by Nippon Kayaku Co., Ltd., acrylic acid (molecular weight: 72.06) ), 2.94 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor and 1.53 g of triphenylphosphine as a reaction catalyst, and the acid of the reaction solution at a temperature of 98 ° C. It was made to react until a value | valence became 0.5 mgKOH / g or less, and the epoxy carboxylate compound (theoretical molecular weight: 510.7) was obtained. Next, 588.2 g of carbitol acetate as a reaction solvent and 105.5 g of dimethylolpropionic acid (molecular weight: 134.16) were added to the reaction solution, and the temperature was raised to 45 ° C. To this solution, 264.7 g of isophorone diisocyanate (molecular weight: 222.28) was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropping, the temperature is raised to 80 ° C., and the reaction is performed for 6 hours until the absorption near 2250 cm ⁻¹ disappears by the infrared absorption spectrum measurement method, and the reaction is further performed for 2 hours at a temperature of 98 ° C. A resin solution containing 60 wt% was obtained. When the acid value was measured, it was 28.9 mgKOH / g (solid content acid value: 48.1 mgKOH / g). Hereinafter, the resin solution of this reaction product is referred to as Varnish A-3.

Synthesis example 4
Orthocresol novolac type epoxy resin (DIC Corporation, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6), 1070 g, diethylene glycol monoethyl ether acetate 600 g, acrylic acid 360 g, and hydroquinone 1.5 g Was heated and stirred at 100 ° C. to uniformly dissolve. Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g of tetrahydrophthalic anhydride were added to the resulting reaction liquid, reacted at 110 ° C. for 4 hours, and after cooling, the solid content acid value 89 mgKOH / g, solid content 65 % Resin solution was obtained. Hereinafter, this resin solution is referred to as Varnish A-4.

Synthesis example 5
A novolac-type cresol resin (manufactured by Showa Polymer Co., Ltd., trade name “Shonol CRG951”, OH equivalent: 119.4) 119. 4 g, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 g of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.1% and the hydroxyl value was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of 1.08 moles of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 g of an alkylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were mixed with a stirrer, a thermometer and an air blowing tube. The reaction vessel was charged with air at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. As the water produced by the reaction, 12.6 g of water was distilled as an azeotrope with toluene. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 g of the obtained novolac acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was blown at a rate of 10 ml / min. While stirring, 60.8 g of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours. A carboxyl group-containing photosensitive resin having a solid acid value of 88 mgKOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this resin solution is referred to as Varnish A-5.

  A photosensitive carboxyl group-containing resin (Nippon Kayaku Co., Ltd. ZFR-1124: solid content 63%, acid value as a resin is 102 mgKOH / g) using a photosensitive group-containing polyfunctional epoxy resin having a bisphenol F structure Using. Hereinafter, this resin solution is designated as varnish A-6.

Preparation of aluminum hydroxide slurry:
700 g of aluminum hydroxide (Hidelite 42M manufactured by Showa Denko KK), 280 g of carbitol acetate and 20 g of BYK-110 (Bicchemy Japan Co., Ltd. wet dispersant) as a solvent were mixed and stirred, and the mixture was stirred in a bead mill. Dispersion treatment was performed using 5 μm zirconia beads. This was repeated three times to produce an aluminum hydroxide slurry that passed through a 3 μm filter.

Examples 1 to 6, Comparative Examples 1 and 2
Using the resin solutions of the above synthesis examples, the various components shown in Table 1 are blended in the proportions (parts by mass) shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and curable resin A composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of each obtained curable resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

Performance evaluation:
<Optimum exposure amount>
The photocurable thermosetting resin compositions of Examples 2 to 6 and Comparative Examples 1 and 2 were applied to the entire surface by screen printing after the circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water and dried. And dried for 30 minutes in a hot air circulation drying oven at 80 ° C. After drying, it is exposed through a step tablet (Kodak No. 2) using an exposure apparatus equipped with a metal halide lamp (HMW-680-GW20) and developed (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution). When the pattern of the step tablet remaining when performing for 60 seconds was 6 steps, the optimum exposure amount was set.

<Resolution>
The photocurable thermosetting resin compositions of Examples 2 to 6 and Comparative Examples 1 and 2 were applied on the front surface of a copper solid substrate by screen printing and dried at 80 ° C. for 30 minutes. Using a negative film of L / S (line / space) = 80/400 μm, exposure is performed with an optimum exposure amount, and development is performed under the above conditions. After development, it was checked whether an 80 μm line remained.
○: An 80 μm line remains on the copper solid substrate.
X: An 80-micrometer line does not remain on a copper solid board | substrate.

<Flexibility (fold resistance)>
The curable resin compositions of the above Examples and Comparative Examples were applied to the entire surface of a 25 μm-thick polyimide film (Kapton 100H manufactured by Toray DuPont Co., Ltd.) by screen printing, dried at 80 ° C. for 30 minutes, and then released to room temperature. Chilled. For the thermosetting resin composition of Example 1, the obtained substrate was cured by heating at 150 ° C. for 60 minutes. For the photocurable thermosetting resin compositions of Examples 2 to 6 and Comparative Examples 1 and 2, the resist was obtained with an optimum exposure amount using an exposure apparatus (HMW-680-GW20) mounted on a metal halide lamp on the obtained substrate. The pattern was exposed, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes.
The obtained evaluation substrate was subjected to 180 ° folding several times by goby folding, and the occurrence of cracks in the coating film at that time was observed visually and with a 200-fold optical microscope, and the number of times that cracks did not occur was determined. evaluated.

<Low warpage>
A sample prepared in the same manner as the sample for evaluation of flexibility (folding resistance) was cut into 50 mm × 50 mm □, and the average value was obtained by measuring the four corners, and evaluated according to the following criteria.
○: The warp is less than 1 mm.
Δ: Warpage is 1 mm or more and less than 4 mm.
X: The warp is 4 mm or more.

<Flame retardance>
The curable resin composition of each example and comparative example was applied to the entire surface of a polyimide film having a thickness of 12.5 μm or 25 μm (Kapton 50H, 100H manufactured by Toray DuPont Co., Ltd.) and dried at 80 ° C. for 20 minutes. And allowed to cool to room temperature. Further, the entire back 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-side coated substrate. About the thermosetting resin composition of Example 1, the obtained board | substrate was heated and cured at 150 degreeC for 60 minutes, and it was set as the test piece. For the photocurable thermosetting resin compositions of Examples 2 to 6 and Comparative Examples 1 and 2, a solder resist was applied at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) mounted on a metal halide lamp on this substrate. The entire surface was exposed, and a 1% Na ₂ CO ₃ aqueous solution at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa. This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. In the evaluation, the flame retardancy test pass was indicated as VTM-0, and the failure was indicated as combustion.
The results of each evaluation test are summarized in Table 2.

  From the results shown in Table 2 above, in the case of the curable resin compositions of Examples 1 to 6, the composition has sufficient low warpage, flexibility, and resolution, and also has excellent flame retardancy. I understand that. On the other hand, in the case of the curable resin composition of Comparative Example 1 that does not contain titanium oxide and Comparative Example 2 that does not contain phosphinic acid metal salt, it is extremely possible to achieve a balance between low warpage, resolution and flame retardancy. I find it difficult.

Examples 7-11
Each photocurable thermosetting resin composition of Examples 2 to 6 shown in Table 1 was prepared by diluting each curable resin composition prepared without blending a silicone-based antifoaming agent with methyl ethyl ketone, and applied onto a carrier film. And dried by heating to form a curable resin composition layer having a thickness of 20 μm, and a cover film was laminated thereon to obtain dry films of Examples 7 to 11, respectively. This dry film was bonded to the test substrate used in the above-described test method using a laminator to produce a test substrate. About the obtained test board | substrate, the evaluation test of each characteristic was done like the evaluation method mentioned above. The results are shown in Table 3.

  From the results shown in Table 3 above, it can be seen that the dry films of Examples 7 to 11 have sufficient low warpage, flexibility and resolution, and also have excellent flame retardancy. . It was found that not only as a curable resin composition but also a dry film and a substrate produced using the dry film were excellent in properties of low warpage, flexibility, resolution, and flame retardancy.

Claims (5)

Carboxyl group-containing resin,
At least one of a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin and a mixture thereof;
A curable resin composition comprising titanium oxide and a phosphinic acid metal salt.   The curable resin composition according to claim 1, wherein the carboxyl group-containing resin is polyurethane.   The dry film formed by apply | coating and drying the curable resin composition of Claim 1 or 2 on a film.   A cured coating film obtained by heat-curing or photo-curing or photo-curing and heat-curing a curable resin composition according to claim 1 or 2 or a dry film formed by applying and drying the curable resin composition on a film. .   A cured coating film obtained by heat-curing or photo-curing or photo-curing and heat-curing a curable resin composition according to claim 1 or 2 or a dry film formed by applying and drying the curable resin composition on a film. A printed wiring board having: