JP2010224171A - Curable resin composition, dry film using the same, and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition containing a halogen-free colorant and a flame retardant and capable of forming a solder resist layer having low warpage and excellent concealment properties of an appearance defect caused by discoloration due to oxidation of a copper circuit, and to provide a dry film using the same and a printed wiring board wherein a flame retardant cured film such as a solder resist is formed by using these. <P>SOLUTION: The curable resin composition contains (A) a carboxyl group containing-resin, (B) titanium oxide and (C) aluminum hydroxide. The curable resin composition further contains (D) a thermosetting component having two or more cyclic ether groups and/or cyclic thioether groups in addition to the components (A) to (C) to form a thermosetting resin composition. The thermosetting resin composition further contains (F) a photopolymerization initiator and (G) a photopolymerizable monomer to form a photocurable thermosetting resin composition, which preferably contains (E) a phosphorus-containing compound. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable resin composition, and more particularly to a curable resin composition capable of forming a solder resist with low warpage and excellent flame retardancy, colorability, and concealability. The present invention also relates to a dry film using such a curable resin composition and a flame retardant printed wiring board.

  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 solder resist, which is a part of these, also requires 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 solder resist 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 on the solder resist is relatively increased.

  For this reason, various proposals have conventionally been made on the flame resistance of solder resist. 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-containing compound having a phosphorus atom in the molecule Photosensitive resin compositions have 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.

  Furthermore, the thin printed circuit board represented by FPC has a problem of warping due to curing shrinkage when the solder resist is photocured or thermally cured.

  On the other hand, the solder resist is formed to protect the copper circuit, but one of its roles is to hide the heat and moisture of the copper circuit, electrical discoloration, scratches and dirt on the copper circuit, etc. There is also an aspect (concealment). In this regard, a colorant is usually added to the solder resist, and it is difficult to see the appearance defect by increasing the concentration.

  Recently, from the viewpoint of reducing environmental impact, solder resists using phthalocyanine blue and yellow colorants that do not have halogen atoms have become widespread, replacing the conventional green colorant chlorinated phthalocyanine green. (For example, refer to Patent Document 2). In addition, phthalocyanine blue is used as a solder resist in blue as it clearly claims that it is halogen-free from the appearance. However, compared with the green color by phthalocyanine green, the blue solder resist ink and the green solder resist ink by the blue colorant and the yellow colorant have a low hiding property and function as a colorant that makes it difficult to see the appearance defects. As described below, it has been found that there are cases where the above cannot be fully achieved.

  That is, the current solder resist is image-cured by photocuring and finally subjected to heat curing treatment. The temperature at this time is appropriate at 150 ° C. for about 30 to 60 minutes, but actually the temperature and time are not constant depending on the substrate manufacturer, and are slightly different. In particular, when the temperature is high and the processing time is long, the substrate using the blue solder resist ink with poor concealment has a problem that the resist cannot conceal the discoloration due to oxidation of the copper circuit, and the substrate looks bad. . This problem can also occur in the green solder resist ink using the halogen-free blue colorant and the yellow colorant as described above, and it has been confirmed by the present inventors that the concealability is weaker than that of phthalocyanine green. . Further, when marking ink is applied on the substrate, since the marking is further printed and thermally cured after the solder resist is cured, the discoloration of the copper circuit is accelerated, and the appearance problem becomes more serious. Furthermore, pressure and heat may be applied in order to compensate for the warpage of the substrate that occurs during the thermal curing of the solder resist. Similarly, discoloration of the circuit is regarded as a problem.

  The most unfavorable phenomenon of discoloration of these copper circuits is that only the edge of the circuit (where the resist is thin) is discolored even on the same copper circuit. In such a state, it becomes defective due to inconsistency with inspection data at the time of inspection and mounting of the substrate. On the other hand, discoloration is recognized, but when it can be recognized as being uniform with other parts on the copper circuit, such a problem does not occur. These defects have been reported previously, but are particularly noticeable when a colorant such as phthalocyanine blue that does not have a halogen atom is used in place of phthalocyanine green (to make the colorant halogen-free). It becomes.

JP 2007-10794 A (Claims) JP 2000-7974 (Claims)

The present invention has been made to solve the problems of the prior art as described above, and its main object is a curable resin composition containing a halogen-free colorant and a flame retardant, and has low warpage. An object of the present invention is to provide a curable resin composition capable of forming a solder resist layer having excellent concealment of appearance defects caused by discoloration due to oxidation of a copper circuit.
Furthermore, the object of the present invention is to use such a curable resin composition to provide a dry film having low warpage, excellent flame retardancy, colorability, and concealment, and a print having a flame retardant coating having such excellent characteristics. It is to provide a wiring board.

In order to achieve the above object, according to the present invention, there is provided a curable resin composition comprising (A) a carboxyl group-containing resin, (B) titanium oxide and (C) aluminum hydroxide. The
In one embodiment, the thermosetting resin composition further comprises (D) a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in the molecule in addition to the above-described components. It can be. In another preferred embodiment, (E) a phosphorus-containing compound is further contained. In another aspect, it can be set as a photocurable thermosetting resin composition by containing (F) a photoinitiator and (G) a photopolymerizable monomer further. In another preferred embodiment, a colorant (H) other than the titanium oxide (B) is contained. In a more preferred embodiment, the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane skeleton, or a carboxyl group-containing resin having a biphenyl novolak structure and an ethylenically unsaturated group, and The thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups is an epoxy resin having a biphenyl novolac skeleton. Such a curable resin composition can be suitably used for forming a solder resist on a printed wiring board.

  Further, according to the present invention, a dry film obtained by applying and drying the curable resin composition on a film, or further obtained by applying and drying the curable resin composition or the curable resin composition on a carrier film. A cured product obtained by thermally curing and / or photocuring the resulting dry film is provided. Furthermore, according to this invention, the printed wiring board which has the said hardened | cured material is also provided.

  The curable resin composition of the present invention contains (B) titanium oxide and (C) aluminum hydroxide together with (A) carboxyl group-containing resin, and preferably further contains (E) phosphorus-containing compound. It is a non-halogen composition, has a low environmental impact, and can form a film having excellent flame retardancy, low warpage, colorability and hiding properties. Therefore, by using the curable resin composition of the present invention, a print having a dry film having low warpage and excellent flame retardancy, colorability, and hiding properties and a flame retardant solder resist film having such excellent characteristics. A wiring board can be provided.

As a result of diligent research to achieve the above-mentioned problems, the present inventors have found that the titanium oxide (A) containing the carboxyl group-containing resin (A) and the aluminum hydroxide (C), which are components of the curable resin composition of the present invention ( B) has found that even when a halogen-free colorant is used, it has the effect of concealing the discoloration of the circuit and at the same time, the effect of reducing the warpage of the cured film. This was a surprising effect that could not be considered at all. Further, when aluminum hydroxide (C) is used in combination with titanium oxide (B), aluminum hydroxide not only acts as a flame retardant, but also has an affinity for a photosensitive resin when it is formed into a photosensitive resin composition. It has been found that the refractive index is close, photocuring can be carried out efficiently, and the decrease in sensitivity and resolution associated with the addition of titanium oxide can be significantly suppressed. Further, when a carboxyl group-containing urethane resin is used as the carboxyl group-containing resin (A), it is effective for low elasticity and low warpage, has an effect of further reducing warpage of the cured film, and further contains a phosphorus-containing compound (E). By containing, flame retardancy can be further improved.
Hereinafter, each component of the curable resin composition of the present invention will be described in detail.

As the carboxyl group-containing resin (A) contained in the curable resin composition of the present invention, a known and commonly used resin compound containing a carboxyl group in the molecule can be used. Further, when the alkali-developable resin composition is used, a carboxyl group-containing resin (A ′) having an ethylenically unsaturated double bond in the molecule is more preferable from the viewpoint of photocurability and development resistance. The unsaturated group is preferably derived from acrylic acid or a methacrylic acid derivative. In addition, when using only the carboxyl group-containing resin which does not have an ethylenically unsaturated double bond, in order to make a composition photocurable, it has two or more ethylenically unsaturated groups in the molecule | numerator mentioned later. It is necessary to use a photopolymerizable monomer (G) in combination.
As specific examples of the carboxyl group-containing resin (A), compounds listed below (any of oligomers and polymers) can be suitably used.

  (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, aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (4) 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 ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.

  (5) During the synthesis of the resin of the above (2) or (4), 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 urethane resin.

  (6) During the synthesis of the resin of (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are present in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (7) dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are reacted with a hydroxyl group present in the side chain by reacting a polyfunctional (solid) epoxy resin as described later. A photosensitive carboxyl group-containing resin to which a product is added.

  (8) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. Functional carboxyl group-containing resin.

  (9) A carboxyl group-containing polyester resin obtained by reacting a difunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

  (10) The resin of the above (1) to (9) further has one epoxy group and one or more (meth) acryloyl groups in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. Photosensitive carboxyl group-containing resin obtained by adding a compound.

Among these carboxyl group-containing resins, preferred are (X) carboxylic group-containing polyurethane resins, particularly those in which the isocyanate group of the urethane resin having an isocyanate group (including diisocyanate) is not directly bonded to the benzene ring, And (Y) the polyfunctional epoxy resin used for the synthesis of the resin is a compound having a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenyl novolac structure, a bisxylenol structure, particularly a biphenyl novolak structure, and a hydrogenated compound thereof. From the viewpoint of low warpage and bending resistance. Also preferred among these are the above copolymer resins and the carboxyl group-containing urethane resins comprising diisocyanates in which the isocyanate groups of the isocyanate group-containing compounds (including diisocyanates) are not directly bonded to the benzene ring. It is particularly preferable for the formation of an alkali-developable composition because it has no yellowing, is effective in concealing properties, and has little ultraviolet absorption.
In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin (A) as described above has a number of free carboxyl groups in the side chain of the backbone polymer, it becomes a crosslinking point during thermosetting. In addition, when a photosensitive composition is used, development with an alkaline aqueous solution becomes possible.
The acid value of the carboxyl group-containing resin (A) is in the range of 10 to 200 mgKOH / g, preferably 30 to 200 mgKOH / g, more preferably 40 to 200 mgKOH / g, particularly preferably 45 to 120 mgKOH / g. It is desirable to be in the range. From the viewpoint of alkali developability, if the acid value of the carboxyl group-containing resin is less than 30 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds. As described above, the line is thin, and in some cases, the exposed portion and the unexposed portion are dissolved and separated by a developer without distinction, and it is difficult to draw a normal resist pattern.

  Moreover, although the weight average molecular weight of the said carboxyl group-containing resin (A) changes with resin frame | skeleton, generally what is in the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is less than 2,000, the heat resistance is insufficient. On the other hand, when the weight average molecular weight exceeds 150,000, the storage stability may be inferior.

  The amount of the carboxyl group-containing resin (A) as described above is 5 to 60% by mass, preferably 10 to 60% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 50%, in the entire composition. % By mass. When the amount is less than the above range, the coating 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.

  As titanium oxide (B) used in the curable resin composition of the present invention, a surface treatment with a sulfuric acid method, a chlorine method, a rutile type titanium oxide, an anatase type titanium oxide, or a hydrous metal oxide, Titanium oxide subjected to surface treatment with an organic compound can be used. Among these titanium oxides (B), rutile type titanium oxide is 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 thermosetting resin composition. In contrast, rutile titanium oxide has a slightly lower whiteness than the anatase type, but has almost no photoactivity, so that a stable solder resist 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 viewpoint of dispersibility in the composition, storage stability, and flame retardancy.

  The blending amount of these titanium oxides (B) is desirably in the range of 0.1 to 200 parts by weight, preferably 1 to 100 parts by weight, more preferably 3 to 100 parts by weight of the carboxyl group-containing resin (A). ~ 80 parts by mass. When the compounding amount of titanium oxide (B) is less than 0.1 parts by mass, good concealability and further low warpage performance cannot be obtained. On the other hand, excessive addition exceeding 200 parts by mass has the property that titanium oxide reflects light in the ultraviolet region, and the refractive index is 2.71, which is a very high value compared to the photosensitive resin. Therefore, a sufficient curing depth as a solder resist cannot be obtained, resulting in poor resolution. In addition, when aluminum hydroxide (C) is not further added in accordance with the present invention, the resolution is significantly lowered.

  Aluminum hydroxide (C) is known as a flame retardant additive, but has an affinity and a refractive index close to those of a photosensitive resin, and is added for efficient photocuring. The titanium oxide is excellent in whiteness and concealment properties, but has a high refractive index (2.71) and strong reflection to ultraviolet rays, so when used in a large amount, it is a thick film (about 10 to 50 μm) like a solder resist. In a photosensitive composition that requires resolution, reduction in sensitivity and resolution is a problem. Therefore, aluminum hydroxide is used together with titanium oxide, and it is used to sufficiently transmit light in the depth direction of the photosensitive resin. By this method, it was possible to improve the resolution of the alkali developing photosensitive composition while maintaining the concealing property. Moreover, the flame retardance requested | required of a soldering resist was also able to be ensured.

  As aluminum hydroxide (C), a publicly known thing can be used, for example, Showa Denko Co., Ltd. Hygilite series, HW, H21, H31, H32, H42M, H43M etc. can be used. 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 blending amount of these aluminum hydroxides (C) is desirably in the range of 1 to 200 parts by weight, preferably 1 to 100 parts by weight, more preferably 10 to 10 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (A). 80 parts by mass. When the blending amount of aluminum hydroxide (C) is less than 1 part by mass, the effect of improving the resolution is not obtained and the flame retardancy is not sufficient. On the other hand, when it is more than 200 parts by mass, the flame retardancy is good, but the flexibility is inferior and the solder heat resistance is also poor.

  As the thermosetting component (D) used for the purpose of improving the properties such as heat resistance and insulation reliability by composing the composition of the present invention into a thermosetting resin composition, the carboxyl group of the carboxyl group-containing resin and Any conventionally known compound having two or more cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the reactable molecule can be used. The above epoxy resins, particularly epoxy resins having a biphenyl novolac skeleton are preferred. Examples of the epoxy resin having a biphenyl novolak skeleton include NC-3000L, NC-3000, NC-3000H, and NC-3100 manufactured by Nippon Kayaku Co., Ltd.

  In addition, the thermosetting component having two or more cyclic (thio) ether groups in the molecule that can be used as the thermosetting component in the thermosetting resin composition of the present invention is 3, 4, or 5 in the molecule. It is a compound having two or more of either a cyclic ether group or a cyclic thioether group of a member ring, or two kinds of groups. For example, a compound having two or more epoxy groups in a molecule, that is, a polyfunctional epoxy compound (D -1), a compound having two or more oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound (D-2), a compound having two or more thioether groups in the molecule, that is, an episulfide resin (D-3), etc. Is mentioned.

  As the polyfunctional epoxy compound (D-1), for example, JER828, JER834, JER1001, JER1004 manufactured by Japan Epoxy Resin, Epicron 840, Epicron 850, Epicron 1050, Epicron 1050, and Epitome 2055 manufactured by Dainippon Ink & Chemicals, Inc. Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Kasei Co., Ltd., D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Ciba Specialty Chemicals' Araldide 6071, Araldide 6084, Araldide GY250, Araldide GY260, Sumitomo Chemical Industries Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei Corporation A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. 664 etc. (all trade names) bisphenol A type epoxy resin; Japan Epoxy Resin JER YL903, Dainippon Ink & Chemicals Epicron 152, Epicron 165, Toto Kasei Epototo YDB-400, YDB- 500, D.C. E. R. 542, Araldide 8011 manufactured by Ciba Specialty Chemicals, Sumi-epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.D. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (all trade names); JER152 and JER154 manufactured by Japan Epoxy Resin, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 from Toto Kasei Co., Ltd., Araldide ECN1235 from Ciba Specialty Chemicals, Araldide ECN1273, Araldide ECN1299, Araldide XPY307, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN- manufactured by Sumitomo Chemical 220, manufactured by Asahi Kasei Corporation. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by Dainippon Ink & Chemicals, JER807 manufactured by Japan Epoxy Resin, Epotot YDF-170 manufactured by Toto Kasei Co., YDF- 175, YDF-2004, Araldide XPY306 manufactured by Ciba Specialty Chemicals, etc. (both trade names); Epototo ST-2004, ST-2007, ST-3000 (trade names, manufactured by Toto Kasei) Hydrogenated bisphenol A type epoxy resin such as JER604 manufactured by Japan Epoxy Resin Co., Epotot YH-434 manufactured by Toto Kasei Co., Ltd., Araldide MY720 manufactured by Ciba Specialty Chemicals Co., Ltd., Sumi-Epoxy ELM manufactured by Sumitomo Chemical Co., Ltd. -120 etc. (both Product name) Glycidylamine type epoxy resin; Ardandide type epoxy resin such as araldide CY-350 (trade name) made by Ciba Specialty Chemicals; Celoxide 2021 made by Daicel Chemical Industries, Araldide made by Ciba Specialty Chemicals CY175, CY179, etc. (both trade names); 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. Xylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 (trade name) manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin; bisphenol A novolac type epoxy resin such as JER157S (trade name) manufactured by Japan Epoxy Resin; JERYL-931 manufactured by Japan Epoxy Resin, Araldide 163 manufactured by Ciba Specialty Chemicals, etc. (all trade names) Tetraphenylolethane type epoxy Fatty; heterocyclic epoxy resins such as Araldide PT810 manufactured by Ciba Specialty Chemicals, TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resins such as ZX-1063 manufactured by Nippon Steel Chemical Co., Ltd .; Naphthalene groups such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by Dainippon Ink and Chemicals, Inc. Containing epoxy resin; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200, HP-7200H manufactured by Dainippon Ink &Chemicals; Glycidyl methacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by Nippon Oil & Fats Co., Ltd. Cyclohexyl maleimide and glycidyl methacrylate Relate copolymerized epoxy resins; epoxy-modified polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), etc. However, it is not limited to these. These epoxy resins can be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound (D-2) include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3- In addition to polyfunctional oxetanes such as ethyl-3-oxetanyl) 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 Scan phenols, 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 episulfide resin (D-3) having two or more 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 blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is preferably 0.6 to 2. with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. It is in the range of 5 equivalents, more preferably 0.8 to 2.0 equivalents. When the blending amount of the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is less than 0.6, carboxyl groups remain in the solder resist film, resulting in 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.

  The curable resin composition of the present invention is a thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule for the purpose of further improving the heat resistance and insulation reliability of the cured coating film. In addition, compounds having two or more isocyanate groups or blocked isocyanate groups in one molecule, amine resins such as melamine resins, melamine derivatives and benzoguanamine resins, cyclocarbonate compounds, bismaleimides, oxazine compounds, oxazoline compounds, A known and commonly used thermosetting resin such as a carbodiimide resin can be blended.

  The compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound, or two or more compounds in one molecule. Examples thereof include compounds having a blocked isocyanate group, that is, blocked isocyanate compounds.

  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 blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methylethyl 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 two or more isocyanate groups or blocked isocyanate groups in one molecule can be used singly or in combination of two or more.
The compounding amount of the compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is 1 to 100 parts by mass, more preferably 100 parts by mass of the carboxyl group-containing resin (A). A ratio of 2 to 70 parts by mass is appropriate. When the amount is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, since the storage stability of a composition falls, it is not preferable.

  Furthermore, examples of other thermosetting components include melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound and the alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, Mw -750LM (manufactured by Sanwa Chemical Co., Ltd.) and the like. The said thermosetting component can be used individually or in combination of 2 or more types.

  When the thermosetting component (D) having two or more cyclic (thio) ether groups in the molecule is used, 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 amount of these thermosetting catalysts to be blended is a normal quantitative ratio, and for example, with respect to 100 parts by mass of the carboxyl group-containing resin (A), preferably 0.1 to 20 parts by mass, more preferably 0.00. 5 to 15.0 parts by mass.

式中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立に、ハロゲン原子以外の置換基を示す。
上記一般式（Ｉ）で表される化合物の市販品としては、ＨＣＡ、ＳＡＮＫＯ−２２０、Ｍ−ＥＳＴＥＲ、ＨＣＡ−ＨＱ（いずれも三光（株）の商品名）等がある The curable resin composition of the present invention preferably contains a phosphorus-containing compound (E). As the phosphorus-containing compound, those conventionally known as organic phosphorus flame retardants may be used, and examples include phosphoric acid esters and condensed phosphoric acid esters, cyclic phosphazene compounds, phosphazene oligomers, and compounds represented by the following general formula (I).

In the formula, R ¹ , R ² and R ³ each independently represent a substituent other than a halogen atom.
Commercially available products of the compound represented by the general formula (I) include HCA, SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sanko Co., Ltd.) and the like.

  Particularly preferred phosphorus-containing compounds (E) used in the present invention include those having (1) acrylate groups as reactive groups, (2) those having phenolic hydroxyl groups, (3) oligomers or polymers, and (4) A phosphazene oligomer is mentioned.

(1) Phosphorus-containing compound having an acrylate group The phosphorus element-containing acrylate is preferably a compound having a phosphorus element and containing two or more (meth) acrylates in the molecule. ) In which R ¹ and R ² are hydrogen atoms, and R ³ 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-containing compound having a phenolic hydroxyl group The phosphorus-containing compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, no deterioration in electrical properties due to hydrolysis, and high solder heat resistance. In addition, as a preferred combination, by using an epoxy resin having a biphenyl skeleton or other epoxy resin as the component (D), 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-containing 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 M-Ester-HP manufactured by Sanko Co., Ltd. and phosphorus-containing Byron 337 manufactured by Toyobo Co., Ltd.

(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. Among them, phenoxyphosphazene oligomers substituted with alkyl groups or polar groups such as hydroxyl groups and cyano groups have high solubility in carboxyl group-containing resins, and there are no problems such as recrystallization even when added in large amounts. preferable.

  The amount of the phosphorus-containing compound (E) as a flame retardant is desirably in the range of 0 to 200 parts by weight, particularly preferably 0 to 100 parts by weight, with respect to 100 parts by weight of the carboxyl group-containing resin (A). is there. If blended in a larger amount than this, the bending properties of the resulting cured film will deteriorate, such being undesirable.

式中、Ｒ^４は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基、若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^５は、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^６及びＲ^７は、それぞれ独立に、炭素数１〜１２のアルキル基又はアリールアルキル基を表し、
Ｒ^８及びＲ^９は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基、又は２つが結合した環状アルキルエーテル基を表し、
Ｒ^１０及びＲ^１１は、それぞれ独立に、炭素数１〜１０の直鎖状又は分岐状のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、又はハロゲン原子、アルキル基若しくはアルコキシ基で置換されたアリール基を表し、但し、Ｒ^１０及びＲ^１１の一方は、Ｒ−Ｃ（＝Ｏ）−基（ここでＲは、炭素数１〜２０の炭化水素基）を表してもよい。 As a photoinitiator (F) used in order to compose a photocurable resin composition, an oxime ester photoinitiator having a group represented by the following general formula (II), the following general formula (III) One or more selected from the group consisting of an α-aminoacetophenone photopolymerization initiator having a group represented by the formula: and / or an acylphosphine oxide photopolymerization initiator having a group represented by the following formula (IV): It is preferable to use a photopolymerization initiator.

In the formula, R ⁴ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ⁵ is a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (which may be substituted with one or more hydroxyl groups). Well, it may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having 1 to 6 carbon atoms) Which may be substituted with an alkyl group or a phenyl group of
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 12 carbon atoms or an arylalkyl group,
R ⁸ and R ⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl ether group in which two are bonded,
R ¹⁰ and R ¹¹ are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or an aryl substituted with a halogen atom, an alkyl group or an alkoxy group. Represents one group, but one of R ¹⁰ and R ¹¹ may represent an R—C (═O) — group (where R is a hydrocarbon group having 1 to 20 carbon atoms).

The oxime ester photopolymerization initiator having a group represented by the general formula (II) is preferably 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the following formula (V), The compound represented by the following general formula (VI) and the compound represented by the following general formula (VII) are mentioned.

式中、Ｒ^１２は、水素原子、ハロゲン原子、炭素数１〜１２のアルキル基、シクロペンチル基、シクロヘキシル基、フェニル基、ベンジル基、ベンゾイル基、炭素数２〜１２のアルカノイル基、炭素数２〜１２のアルコキシカルボニル基（アルコキシル基を構成するアルキル基の炭素数が２以上の場合、アルキル基は１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、又はフェノキシカルボニル基を表し、
Ｒ^１３、Ｒ^１５は、それぞれ独立に、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表し、
Ｒ^１４は、水素原子、フェニル基（炭素数１〜６のアルキル基、フェニル基若しくはハロゲン原子で置換されていてもよい）、炭素数１〜２０のアルキル基（１個以上の水酸基で置換されていてもよく、アルキル鎖の中間に１個以上の酸素原子を有していてもよい）、炭素数５〜８のシクロアルキル基、炭素数２〜２０のアルカノイル基又はベンゾイル基（炭素数が１〜６のアルキル基若しくはフェニル基で置換されていてもよい）を表す。

In the formula, R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 alkoxycarbonyl groups (when the alkyl group constituting the alkoxyl group has 2 or more carbon atoms, the alkyl group may be substituted with one or more hydroxyl groups, and one or more oxygen atoms are placed in the middle of the alkyl chain. Which may have), or a phenoxycarbonyl group,
R ¹³ and R ¹⁵ are each independently a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), an alkyl group having 1 to 20 carbon atoms (one or more Which may be substituted with a hydroxyl group and may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (Which may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group),
R ¹⁴ represents a hydrogen atom, a phenyl group (which may be substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom), or an alkyl group having 1 to 20 carbon atoms (substituted with one or more hydroxyl groups). And may have one or more oxygen atoms in the middle of the alkyl chain), a cycloalkyl group having 5 to 8 carbon atoms, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group (having a carbon number). 1-6 alkyl groups or phenyl groups optionally substituted).

式中、Ｒ^１６、Ｒ^１７及びＲ^２２は、それぞれ独立に、炭素数１〜１２のアルキル基を表し、
Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表し、
Ｍは、Ｏ、Ｓ又はＮＨを表し、
ｍ及びｐは、それぞれ独立に０〜５の整数を表す。

In the formula, R ¹⁶ , R ¹⁷ and R ²² each independently represent an alkyl group having 1 to 12 carbon atoms,
R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
M represents O, S or NH;
m and p each independently represents an integer of 0 to 5.

  Among the oxime ester photopolymerization initiators, 2- (acetyloxyiminomethyl) thioxanthen-9-one represented by the general formula (V) and a compound represented by the formula (VI) are more preferable. Examples of commercially available products include CGI-325 manufactured by Ciba Specialty Chemicals, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, and the like. These oxime ester photopolymerization initiators can be used alone or in combination of two or more.

  As the α-aminoacetophenone photopolymerization initiator having a group represented by the general formula (III), 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 Specialty Chemicals.

  Examples of the acylphosphine oxide photopolymerization initiator having the group represented by the general formula (IV) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine. Examples thereof include oxides and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF and Irgacure 819 manufactured by Ciba Specialty Chemicals.

  Of the above-mentioned photopolymerization initiators, an acylphosphine oxide-based initiator having a group represented by the general formula (IV) is particularly preferable, and it has the best light transmittance from the photobleaching performance and is flame retardant. Has an effect on sex. In addition, the oxime ester-based initiator having the group represented by the general formula (II) has good initiator efficiency and is effective in improving sensitivity in a small amount, so that there is little outgas during the heat treatment after forming the resist film. It is preferable because it is effective in reducing the warpage of the film. Particularly preferred is a combination of both.

The amount of the photopolymerization initiator (F) as described above is in the range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). Is appropriate. When the blending amount of the photopolymerization initiator (F) is less than 0.01 parts by mass, the photocurability on copper is insufficient, and the coating film is peeled off or the coating properties such as chemical resistance are deteriorated. It is not preferable. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the solder resist coating film of the photopolymerization initiator (F) becomes intense and the deep curability tends to decrease, which is not preferable.
In the case of the oxime ester photopolymerization initiator having a group represented by the formula (II), the blending amount thereof is preferably 0.01 to 100 parts by mass of the carboxyl group-containing resin (A). 20 mass parts, More preferably, the range of 0.01-5 mass parts is desirable.

  Other photopolymerization initiators, photoinitiator assistants, and sensitizers that can be suitably used in the photocurable resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, and benzophenones. A compound, a xanthone compound, a tertiary amine 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, and 1,1-dichloroacetophenone.

Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.
Specific examples of the thioxanthone compound include, for example, 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, for example, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, 4-benzoyl-4′-propyldiphenyl. Sulfide.

  Specific examples of the tertiary amine compound include, 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.), 4,4′-diethylamino. Dialkylamino benzophenone such as benzophenone (EAB manufactured by Hodogaya Chemical Co.), and dialkylamino groups such as 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin) Containing coumarin compound, ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics), 4-dimethylaminobenzoic acid ( -Butoxy) ethyl (Quantacure BEA, manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), 4,4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

Among the above-mentioned compounds, thioxanthone compounds and tertiary amine compounds are preferable. The composition of the present invention preferably contains a thioxanthone compound from the viewpoint of deep curable properties. Among them, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone A thioxanthone compound such as
The amount of such a thioxanthone compound is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the carboxyl group-containing resin (A). If the amount of the thioxanthone compound is too large, the thick film curability is lowered and the cost of the product is increased, which is not preferable.

  As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. The dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm has a maximum absorption wavelength in the ultraviolet region, so that it is less colored and uses a colored pigment as well as a colorless and transparent photosensitive composition. A colored solder resist film reflecting the color can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). It is. When the amount of the tertiary amine compound is less than 0.1 parts by mass, a sufficient sensitizing effect tends not to be obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep curability tends to decrease.

  In the photocurable resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole, and the like can be used as chain transfer agents in order to improve sensitivity. 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.

  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- Examples include 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, and 2-mercapto-6-hexanolactam.

  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, 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.

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 in a range of 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin (A). When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  The photopolymerizable monomer (G) used for composing the composition of the present invention into a photocurable resin composition is photocured by irradiation with active energy rays, and the photocurable resin composition of the present invention is obtained. It helps insolubilize or insolubilize in an alkaline aqueous solution. Examples of such compounds include glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, and the like. Polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols Glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycy Ethers, polyvalent acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylate, and / or the like each methacrylates corresponding to the acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, and further, 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 blending amount of the photopolymerizable monomer (G) having two or more ethylenically unsaturated groups in such a molecule is 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A), More preferably, it is a ratio of 1 to 70 parts by mass. 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.

  The curable resin composition of this invention can mix | blend a coloring agent (H). As the colorant (H), 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 Dyers 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, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151 , 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.
Disazo: Pigment Red 37, 38, 41.
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1,68.
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.
Perylene series: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.
Diketopyrrolopyrrole series: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.
Condensed azo series: 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.
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:
Blue colorants include phthalocyanine and anthraquinone, and pigments are compounds 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, Pigment Blue 60.
The dye systems include Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, there are phthalocyanine, anthraquinone, and perylene types as green colorants. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. 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 type: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.
Condensed azo series: 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: 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, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The blending ratio of the colorant (H) as described above is not particularly limited, but is preferably 0 to 10 parts by mass, particularly preferably 0.1 to 100 parts by mass of the carboxyl group-containing resin (A). A proportion of 5 parts by weight is sufficient.

  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, known and commonly used inorganic or organic fillers can be used. In particular, barium sulfate, spherical silica and talc are preferably used. Moreover, magnesium hydroxide, boehmite, etc. can be used for the purpose of imparting flame retardancy. Furthermore, NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nano silica is dispersed in the compound having one or more ethylenically unsaturated groups or the polyfunctional epoxy resin. , XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all are product grade names) manufactured by Hanse-Chemie . These may be used alone or in combination of two or more.

  The blending 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 (A). Part. 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.

  In the curable resin composition of the present invention, conventionally known binder polymers can be used for the purpose of improving flexibility and dryness to touch. As the binder polymer, cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., a polyester-based polymer byron series manufactured by Toyobo Co., Ltd., and a phenoxy resin-based polymer as bisphenol A, Bisphenol F and phenoxy resins of their hydrogenated compounds are preferred. The addition amount of these binder polymers is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). When the blending amount of the binder polymer exceeds 50 parts by mass, the alkali developability of the curable resin composition is inferior and the usable potable time for development is shortened.

  In the curable resin composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the photosensitive resin layer and the substrate. Specific examples include, for example, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2- Thion, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, etc. is there.

  Generally, in many polymer materials, once oxidation starts, oxidative degradation occurs successively in sequence, resulting in a decrease in the function of the polymer material. Therefore, the curable resin composition of the present invention prevents oxidation. (1) A radical scavenger that invalidates the generated radicals and / or (2) a peroxide decomposer that decomposes the generated peroxide into harmless substances and prevents the generation of new radicals. An antioxidant can be added.

  Specific examples of the antioxidant that acts as a radical scavenger 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) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6) Tetramethyl-4-piperidyl) - 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 152, TINUVIN 152, TINUVIN 292, TINUVIN 5100 Special 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 (manufactured by Asahi Denka Co., Ltd., trade name), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilyzer TPS (Sumitomo Chemical) Company name, product name).
Said antioxidant can be used individually by 1 type or in combination of 2 or more types.

  In general, since the polymer material absorbs light and thereby decomposes and deteriorates, the curable resin composition of the present invention includes, in addition to the above antioxidant, in order to take a countermeasure against stabilization against ultraviolet rays. UV absorbers can be used.

  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 Specialty Chemicals, Inc., trade name).
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 molding obtained from the curable resin composition of this invention is possible. I can plan.

  Furthermore, the curable resin composition of the present invention uses an organic solvent for the synthesis of the carboxyl group-containing resin (A), the adjustment of the composition, or the adjustment of the viscosity for application to a substrate or a carrier film. be able to.

  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.

  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 to prevent thermal polymerization or temporal polymerization 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, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

The curable resin composition of this invention can also be made into the form of the dry film provided with the carrier film (support body) and the layer which consists of the said curable resin composition formed on this carrier film.
When forming a dry film, the curable resin composition of the present invention is diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater. A film can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After the film is formed on the carrier film, it is desirable to further laminate a peelable cover film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.
As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  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. Further, in the case of a dry film obtained by applying the above composition on a carrier film and drying and winding it as a film, after laminating the curable resin composition layer on the substrate with a laminator or the like The resin insulating layer can be formed by peeling off the carrier film.

  In the case of a photo-curable resin composition, after that, by a contact type (or non-contact type), selectively exposed with an active energy ray through a photomask on which a pattern is formed or directly exposed with a laser direct exposure machine, and unexposed. The portion is developed with a dilute alkaline aqueous solution (for example, 0.3 to 3 wt% sodium carbonate aqueous solution) to form a resist pattern. Further, in the case of a composition containing a thermosetting component (D), for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the carboxyl group-containing resin (A) and molecules A thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups reacts, and has excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties. A cured coating film can be formed. In addition, even when the thermosetting component (D) is not contained, by performing heat treatment, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization, and the coating film characteristics are improved. Depending on the purpose and application, heat treatment (thermosetting) may be performed.

  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.
In the case of a photocurable resin composition, the exposed portion (the portion irradiated with the active energy ray) is exposed (irradiated with active energy rays) to the coating film obtained after being applied and the solvent is evaporated and dried. ) Is cured.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, 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 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 800 mJ / cm ² , preferably 20 to 600 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.

  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. In the following description, “parts” and “%” are based on mass unless otherwise specified.

Synthesis example 1
(A-1) Synthesis of a resin corresponding to the carboxyl group-containing resin (2):
A polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol as a compound having two or more alcoholic hydroxyl groups in a reaction vessel equipped with a stirrer, a thermometer and a condenser (Asahi Kasei Chemicals Corporation) ), TJ5650J, number average molecular weight 800) 3600 g (4.5 mol), dimethylolbutanoic acid 814 g (5.5 mol), and n-butanol 118 g (1. 6 mol) was charged. 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.

Synthesis example 2
(A-2) Synthesis of a resin corresponding to the carboxyl group-containing resin (5):
2400 g of polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (TJ5650J, number average molecular weight 800, manufactured by Asahi Kasei Chemicals Corporation) in a reaction vessel equipped with a stirrer, a thermometer and a condenser. (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.

Synthesis example 3
(A-3) Synthesis of a resin corresponding to the carboxyl group-containing resin (4):
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) 142.7 g, 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, 2.94 g, and 1.53 g of triphenylphosphine as a reaction catalyst, were charged at a temperature of 98 ° C. It was made to react until an acid value became 0.5 mgKOH / g or less, and the epoxy carboxylate compound (a) (theoretical molecular weight: 510.7) was obtained. Next, 588.2 g of carbitol acetate and 105.5 g of dimethylolpropionic acid (b) (molecular weight: 134.16) were added to the reaction solution as a reaction solvent, and the temperature was raised to 45 ° C. To this solution, 264.7 g of isophorone diisocyanate (c) (molecular weight: 222.28) was gradually added dropwise so that the reaction temperature did not exceed 65 ° C. After completion of the dropwise addition, the temperature is raised to 80 ° C., and the reaction is performed for 6 hours until absorption near 2250 cm ⁻¹ disappears by infrared absorption spectrum measurement, 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).

(A-4) Resin corresponding to the carboxyl group-containing resin (7):
It corresponds to the carboxyl group-containing resin (7) and is a photosensitive carboxyl group-containing resin using a polyfunctional epoxy having a photosensitive group-containing biphenyl novolac structure [Nippon Kayaku Co., Ltd. ZCR-1601H (solid content 65%, as resin) The acid value of 98 mgKOH / g) was used.

Preparation of aluminum hydroxide slurry:
700 g of aluminum hydroxide (Heidilite 42M manufactured by Showa Denko KK) and 280 g of Calbitoacetate and 20 g of BYK-110 as a solvent were mixed and stirred, and dispersion treatment was performed using 0.5 μm zirconia beads in a bead mill. This was repeated three times to produce an aluminum hydroxide slurry (C-1) that passed through a 3 μm filter.

Examples 1-11, Comparative Examples 1-3
Using the resin solutions of the respective synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and used for solder resist A photosensitive resin composition was prepared. Here, it was 15 micrometers or less when the dispersion degree of the obtained photosensitive resin composition was evaluated by the particle size measurement by the Grindometer by Eriksen.

Performance evaluation:
<Optimum exposure amount>
The thermosetting / photocurable resin compositions of Examples 2 to 11 and Comparative Examples 2 and 3 were washed with water after buffing a circuit pattern substrate having a copper thickness of 35 μm, dried, and then screen-printed on the entire surface. It is applied and dried in a hot air circulation drying oven at 80 ° C. for 30 minutes. 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 manufactured by Oak Manufacturing Co., Ltd.) and developed (30 ° C., 0.2 MPa, 1 wt%). When the pattern of the step tablet remaining when the Na ₂ CO ₃ aqueous solution was performed for 90 seconds was 6 steps, the optimum exposure amount was set.

Characteristic test:
The compositions of Examples 1 to 11 and Comparative Examples 1 to 3 were applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The thermosetting resin compositions of Example 1 and Comparative Example 1 were cured by heating the obtained substrates at 150 ° C. for 60 minutes. For the photocurable resin compositions of Examples 2 to 11 and Comparative Examples 2 and 3, a solder resist pattern was formed at an optimal exposure amount using an exposure apparatus (HMW-680-GW20) mounted on a metal halide lamp on the obtained substrate. The resist was exposed to light and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 90 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Circuit concealment>
The substrate obtained as described above is further heated at 140 ° C. for 1 hour. It was confirmed whether the color of the copper circuit in the portion covered with the solder resist was changed by heating at 140 ° C. for 1 hour.
○: No discoloration of copper circuit ×: Disappearance of copper circuit discoloration

<Solder heat resistance>
The evaluation board | substrate which apply | coated the rosin-type flux was immersed in the solder tank previously set to 260 degreeC, and after washing | cleaning the flux with denatured alcohol, the swelling / peeling of the resist layer by visual observation was evaluated. The judgment criteria are as follows.
○: No peeling is observed after being immersed once for 10 seconds. Δ: No peeling is observed after being immersed once for 5 seconds. ×: The resist layer is swollen after being immersed once for 5 seconds.

<Low warpage>
A cured film produced on Kapton 100H (a polyimide film manufactured by Toray DuPont Co., Ltd., thickness: 25 μm) was cut out to 50 × 50 mm, an average value was determined by measuring four-angle warpage, and evaluated according to the following criteria.
○: Warpage is less than 1 mm Δ: Warpage is 1 mm or more and less than 4 mm ×: Warpage is 4 mm or more

<Resolution>
The photosensitive resin compositions of Examples 2 to 11 and Comparative Examples 2 and 3 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) = 100/500 μm, the film is exposed at the optimum exposure amount and developed under the above conditions. After development, check if 100 μm lines remain.
○: A 100 μm line remains on the copper solid substrate.
X: A 100-micrometer line does not remain on a copper solid board | substrate.

<Flame retardance>
The 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.) by screen printing, dried at 80 ° C. for 20 minutes, and room temperature. It was left to cool. 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. The thermosetting resin compositions of Example 1 and Comparative Example 1 were cured by heating the obtained double-sided coated substrate at 150 ° C. for 60 minutes. For the photocurable resin compositions of Examples 2 to 11 and Comparative Examples 2 and 3, a solder resist with an optimal exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp on the obtained double-sided coated substrate. Were exposed to light, developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. for 90 seconds under the condition of a spray pressure of 0.2 MPa, and thermally cured at 150 ° C. for 60 minutes to obtain an evaluation sample. This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. Evaluation was expressed as VTM-0 or VTM-1 based on the UL94 standard.

The results of each evaluation test are summarized in Table 2.

Example 12
A curable resin composition prepared by blending the composition shown in Example 3 shown in Table 1 without adding a silicone-based antifoaming agent was diluted with methyl ethyl ketone, applied onto a carrier film, heat-dried, and a thickness of 20 μm. A photosensitive resin composition layer was formed, and a cover film was laminated thereon to obtain a dry film. Thereafter, the cover film was peeled off, and the film was bonded to the patterned copper foil substrate using a laminator to prepare a test substrate. In the same manner as the test method and the evaluation method described above, an evaluation test of each characteristic was performed. The results are shown in Table 3.

Claims (12)

  A curable resin composition comprising (A) a carboxyl group-containing resin, (B) titanium oxide, and (C) aluminum hydroxide.   The curable resin composition according to claim 1, further comprising (D) a thermosetting component having two or more cyclic ether groups and / or cyclic thioether groups in the molecule.   Furthermore, (E) phosphorus containing compound is contained, The curable resin composition of Claim 1 or 2 characterized by the above-mentioned.   The curable resin composition according to claim 1, further comprising (F) a photopolymerization initiator and (G) a photopolymerizable monomer.   The curable resin composition according to any one of claims 1 to 4, further comprising a colorant (H) other than the titanium oxide (B).   The curable resin composition according to claim 1, wherein the carboxyl group-containing resin (A) is a carboxyl group-containing resin having a urethane skeleton.   The curable resin composition according to any one of claims 1 to 5, wherein the carboxyl group-containing resin (A) has a biphenyl novolak structure and an ethylenically unsaturated group.   8. The thermosetting component (D) having two or more cyclic ether groups and / or cyclic thioether groups in the molecule is an epoxy resin having a biphenyl novolak skeleton. The curable resin composition according to one item.   The curable resin composition according to claim 1, wherein the curable resin composition is a solder resist.   The dry film formed by apply | coating and drying the curable resin composition as described in any one of Claims 1 thru | or 9 on a film.   The curable resin composition according to any one of claims 1 to 9, or a dry film obtained by applying and drying the curable resin composition on a carrier film is thermally cured and / or photocured. The cured product obtained.   A printed wiring board having the cured product according to claim 11.