JP5806492B2 - Curable resin composition, dry film and printed wiring board using the same - Google Patents

Description

  The present invention relates to a curable resin composition, a dry film and a printed wiring board using the same, and more specifically, a curable resin composition capable of forming a cured film excellent in resolution and reflection characteristics, and The present invention relates to a dry film and a printed wiring board using the above.

  In recent years, light-emitting diodes (LEDs) are rapidly spreading as light sources with low power consumption and long life due to demands for energy saving of electric appliances. The LED is used as a backlight of a liquid crystal display such as a portable terminal, a personal computer, a television, or a light source of a lighting fixture. At that time, an LED of a type that is directly mounted on a printed wiring board coated with a solder resist film, So-called surface mount LEDs are increasingly being used.

  In surface-mounted LEDs, printed wiring boards having a high-reflectance solder resist film are required in order to efficiently use the light from the LEDs. A white solder resist using titanium has been proposed.

Japanese Patent No. 4340272

  However, the curable resin composition containing a large amount of a pigment having a high refractive index and reflecting light, such as titanium oxide, has room for further improvement in resolution.

  Accordingly, an object of the present invention is to provide a curable resin composition capable of forming a cured film excellent in resolution and reflection characteristics, a dry film and a printed wiring board using the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a curable resin composition containing a specific filler, and have completed the present invention. .

  That is, the curable resin composition of the present invention contains a filler obtained by firing a hydrous silicate mineral containing (A) a carboxyl group-containing resin, (B) titanium oxide, and (C) aluminum or magnesium. To do.

  The curable resin composition of the present invention preferably further contains a thermosetting component.

  Moreover, it is preferable that the curable resin composition of this invention contains a photoinitiator and a photosensitive monomer further.

  In the curable resin composition of the present invention, it is preferable that the filler obtained by firing the hydrous silicate mineral containing (C) aluminum or magnesium is fired Neuburg silica particles.

  Moreover, it is preferable that the curable resin composition of this invention is a soldering resist.

  The dry film of the present invention is characterized in that any one of the above curable resin compositions is applied to a film and dried.

  The cured film of the present invention is obtained by heat-curing and / or photocuring any one of the above-described curable resin compositions or dry films.

  The printed wiring board of the present invention is characterized by comprising the above-described cured film.

  According to the present invention, when the photocurable composition is excellent in reflection characteristics, a curable resin composition excellent in resolution, a dry film and a printed wiring board using the same can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
The curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B) titanium oxide, and (C) a filler obtained by firing a hydrous silicate mineral containing aluminum or magnesium. It is. (A) Alkali development is possible by containing a carboxyl group-containing resin. Curing may be performed by thermal curing, photocuring, or thermal curing and photocuring, but is preferably a photocurable curable resin composition. (A) The carboxyl group-containing resin is a carboxyl group-containing resin having a photopolymerizable unsaturated double bond, or can further be made photocurable by further containing a photopolymerizable monomer described later. . Moreover, since it is excellent in the reflective property of the light of this invention, it is preferable that it is white.
Hereinafter, each component will be described in detail.

[(A) Carboxyl group-containing resin]
As said (A) carboxyl group containing resin, resin containing a well-known carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. From the viewpoint of photocurability and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group, but only a carboxyl group-containing resin having no ethylenically unsaturated bond ( It can also be used as component A). In order to make the composition photocurable when the resin of component (A) does not have an ethylenically unsaturated bond, a compound (photosensitive monomer having one or more ethylenically unsaturated groups in the molecule) ) Must be used in combination. As the ethylenically unsaturated bond, those derived from acrylic acid, methacrylic acid or derivatives thereof are preferable.
Further, as the component (A), it is preferable to use a carboxyl group-containing resin that does not use an epoxy resin as a starting material. A carboxyl group-containing resin that does not use an epoxy resin as a starting material has a very low halide ion content, and can suppress deterioration in insulation reliability.

Specific examples of the carboxyl group-containing resin that can be used in the curable resin composition of the present invention include the compounds listed below (any of oligomers and polymers).
(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers 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) Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a product with a polybasic acid anhydride.
(11) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
(12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
(13) One epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate and the like in any one of the resins (1) to (12) above A photosensitive carboxyl group-containing resin obtained by adding a compound having a group.

Among the carboxyl group-containing resins, preferred are the above-mentioned copolymer resin (1), the above-mentioned carboxylic group-containing polyurethane resin, particularly the isocyanate group of the urethane resin having an isocyanate group (including diisocyanate) directly on the benzene ring. It is a carboxyl group-containing urethane resin composed of unbonded diisocyanate.
The carboxyl group-containing urethane resin composed of diisocyanate in which the isocyanate group of the component having an isocyanate group (including diisocyanate) is not directly bonded to the benzene ring is suppressed in yellowing, effective for concealment, and has little ultraviolet absorption. It is characterized by excellent resolution and low warpage when used as an alkali-developable composition.

  Further, when 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 biphenol novolak structure, a bisxylenol structure, particularly a biphenyl novolak structure, and a hydrogenated compound thereof, The cured product of the curable resin composition to be obtained is preferable because of low warpage and excellent bending resistance.

  Here, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

  The (A) carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, and therefore can be developed with an alkaline aqueous solution.

  Moreover, the acid value of the said carboxyl group-containing resin has the preferable range of 20-200 mgKOH / g, More preferably, it is the range of 40-150 mgKOH / g. If the acid value of the carboxyl group-containing resin is less than 20 mgKOH / g, adhesion of the coating film may not be obtained, or alkali development may be difficult in the case of a photocurable resin composition. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, so that the line becomes thinner than necessary. In some cases, the developer is not distinguished between the exposed portion and the unexposed portion May cause dissolution and peeling, making it difficult to draw a normal resist pattern.

  Although the weight average molecular weight of the (A) carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, it is generally preferably 2,000 to 150,000. When the weight average molecular weight is less than 2,000, tack-free performance may be inferior, the moisture resistance of the coated film after exposure may be poor, film thickness may be reduced during development, and resolution may be greatly inferior. On the other hand, when the weight average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior. More preferably, it is 5,000-100,000.

  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 in the entire curable resin composition of the present invention. Especially preferably, it is 30-50 mass%. When the amount is less than the above range, the coating film strength may decrease, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity of the composition may increase or the coating property may decrease, which is not preferable.

[(B) Titanium oxide]
Moreover, as (B) titanium oxide used by this invention, although a rutile type titanium oxide or an anatase type titanium oxide may be sufficient, it is preferable to use a rutile type titanium. Anatase-type titanium oxide, which is the same titanium oxide, has higher whiteness compared to rutile-type titanium oxide and is often used as a white pigment. The emitted light may cause discoloration of the resin in the insulating resin composition. In contrast, rutile-type titanium oxide is slightly inferior to anatase-type in whiteness, but has almost no photoactivity, so that the resin is deteriorated by light due to the photoactivity of titanium oxide (yellowing). Is remarkably suppressed and is stable against heat. For this reason, when it is used as a white pigment in the insulating layer of the printed wiring board on which the LED is mounted, a high reflectance can be maintained over a long period of time.

  A well-known thing can be used as a rutile type titanium oxide. There are two types of production methods for rutile titanium oxide, a sulfuric acid method and a chlorine method. In the present invention, those produced by any of the production methods can be suitably used. Here, the sulfuric acid method uses ilmenite ore or titanium slag as a raw material, dissolves this in concentrated sulfuric acid, separates iron as iron sulfate, and hydrolyzes the solution to obtain a hydroxide precipitate. A production method in which rutile titanium oxide is taken out by baking at a high temperature. On the other hand, the chlorine method uses synthetic rutile or natural rutile as a raw material, reacts with chlorine gas and carbon at a high temperature of about 1000 ° C to synthesize titanium tetrachloride, and oxidizes this to extract rutile titanium oxide. Say. Among them, rutile-type titanium oxide produced by the chlorine method is particularly effective in suppressing the deterioration (yellowing) of the resin due to heat, and is more preferably used in the present invention.

  Examples of commercially available rutile-type titanium oxides include, for example, Typek R-820, Typek R-830, Typek R-930, Typek R-550, Typek R-630, Typek R-680, Typek R-670, and Typek R. -680, Type R-670, Type R-780, Type R-850, Type CR-50, Type CR-57, Type CR-80, Type CR-90, Type CR-93, Type CR-95, Type CR -97, Type CR-60, Type CR-63, Type CR-67, Type CR-58, Type CR-85, Type UT771 (Ishihara Sangyo Co., Ltd.), Type Pure R-100, Type Pure R-101, Type Pure R -102, Ipure R-103, Taipure R-104, Taipure R-105, Taipure R-108, Taipure R-900, Taipure R-902, Taipure R-960, Taipure R-706, Taipure R-931 (manufactured by DuPont) , R-25, R-21, R-32, R-7E, R-5N, R-61N, R-62N, R-42, R-45M, R-44, R-49S, GTR-100, GTR -300, D-918, TCR-29, TCR-52, FTR-700 (manufactured by Sakai Chemical Industry Co., Ltd.) and the like can be used.

  Among them, the Taipei CR-50, the Taipei CR-57, the Taipei CR-80, the Taipei CR-90, the Taipei CR-93, the Taipei CR-95, the Taipei CR-97, the Taipei CR-60, and the Taipei manufactured by the chlorine method. CR-63, Taipei CR-67, Taipei CR-58, Taipei CR-85, Taipei UT771 (manufactured by Ishihara Sangyo Co., Ltd.), Taipei Pure R-100, Taiwan Pure R-101, Taiwan Pure R-102, Taiwan Pure R-103, Taiwan Pure R-104, Tai Pure R-105, Tai Pure R-108, Tai Pure R-900, Tai Pure R-902, Tai Pure R-960, Tai Pure R-706, Tai Pure R-931 (manufactured by DuPont Co., Ltd.) can be used more preferably. .

  Moreover, as an anatase type titanium oxide, a well-known thing can be used. Commercially available anatase-type titanium oxides include TITON-110, TITON TCA-123E, TITON A-190, TITON A-197, TITON SA-1, TITONSA-1L (manufactured by Sakai Chemical Industry Co., Ltd.), TA-100. , TA-200, TA-300, TA-400, TA-500, TP-2 (manufactured by Fuji Titanium Industry Co., Ltd.), TITANIX JA-1, TITANIX JA-3, TITANIX JA-4, TITANIX JA-5, TITANIX JA -C (manufactured by Teika Co., Ltd.), KA-10, KA-15, KA-20, KA-30 (manufactured by Titanium Industry Co., Ltd.), Taipei A-100, Taipei A-220, Taipei W-10 (Ishihara Sangyo) Etc.) can be used.

  Among these titanium oxides, it is particularly preferable to use titanium oxide whose surface is treated with hydrous alumina or aluminum hydroxide from the viewpoints of dispersibility in the composition, storage stability, and flame retardancy.

  The blending amount of these titanium oxides is desirably in the range of 0.1 to 300 parts by weight, preferably 1 to 200 parts by weight, more preferably 3 to 150 parts by weight with respect to 100 parts by weight of the carboxyl group-containing resin (A). Part. When the blending amount of titanium oxide is less than 0.1 part by weight, performance such as good reflection characteristics may not be obtained. Further, excessive addition of 200 parts by mass or more 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. In some cases, a sufficient curing depth cannot be obtained as a solder resist, resulting in poor resolution.

  In addition, the filler which baked the hydrous silicate mineral containing (C) aluminum or magnesium of this invention can suppress the fall of the resolution by the above mass mixing of a titanium oxide.

[(C) a filler obtained by firing a hydrous silicate mineral containing aluminum or magnesium]
The filler obtained by firing the hydrous silicate mineral containing (C) aluminum or magnesium used in the present invention is composed of a hydrous silicate mineral as a main component, and a naturally occurring clay mineral is fired in a firing furnace. An anhydrous silicate mineral containing aluminum or magnesium from which moisture has been removed. The firing temperature is preferably 600 to 1300 ° C, more preferably 600 to 1000 ° C.
By using a filler obtained by firing a hydrous silicate mineral containing aluminum or magnesium, a curable resin composition exhibiting good whiteness and resolution can be obtained. This is considered to be because the refractive index of the filler obtained by baking the hydrous silicate mineral containing aluminum or magnesium is close to that of the photosensitive resin, so that light can be sufficiently transmitted in the depth direction of the photosensitive resin. It is done.

  Specific examples of the component (C) include calcined kaolin clay, calcined talc, and calcined Neuburg silica. When the amount of the filler obtained by firing the hydrated silicate mineral containing aluminum or magnesium is large, the coating film may be semi-glossy. This is considered to be caused by familiarity with the resin. The calcined Neuburg silica is a calcined product of a natural combination of amorphous silica and platy kaolinite, and its surface is covered with a very fine silica component. Even if the salt mineral is used in the same manner as the fired filler, the gloss can be maintained, and the surface treatment can be easily performed, which is preferable.

(C) As a filler obtained by firing a hydrous silicate mineral containing aluminum or magnesium, a generally known filler can be used. Examples of commercially available products include the following. As calcined kaolin clay, GlomaxLL, PoleSter400, PoleSter200R, PoleSterLD, PoleSter501, PoleSter102A, PoleSter103A, PoleSter402, Alphatex, Opacitex, Transfring 37, BASF Link 45, Transf link 45, manufactured by ISF Minerals Japan, Inc. Translink 555, Translink HF-900, Translink PA100, Satinton 5, Satinton 5HB, Satinton SPECIAL, Satinton W, Satinton PLUS, Satinton SP-33, Ultrex 95, Ultrex 96, Mattex, Metamax, MetamaxFF, etc. Can be mentioned. As the calcined talc, CTH-125, BST, ST-95, ST-2000 manufactured by Nippon Talc Co., Ltd. can be used.
An example of the fired Neuburg silica is Sylfit Z91 manufactured by Hoffman Minerals.

(C) As for the compounding quantity of the filler which baked the hydrous silicate mineral containing aluminum or magnesium, 1-100 mass parts is preferable with respect to 100 mass parts of (B) titanium oxide, and 5-80 mass parts is more preferable. 10 to 50 parts by mass is more preferable.
(C) If the amount of the filler obtained by firing the hydrous silicate mineral containing aluminum or magnesium is less than 1 part by mass, the effect of improving the resolution may not be seen, and the excess exceeds 80 parts by mass. Addition may cause a decrease in whiteness and hiding.

(Thermosetting component)
Furthermore, a thermosetting component can be added to the curable resin composition of the present invention in order to impart heat resistance. Examples of the thermosetting component used in the present invention include known and commonly used blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, and the like. A thermosetting resin etc. are mentioned. Among these, a preferable thermosetting component is a thermosetting component having a plurality of cyclic ether groups and / or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule. There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.

  Such a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes either one of a three-, four- or five-membered cyclic ether group or a cyclic thioether group or two kinds of groups in the molecule. A compound having a plurality of epoxy groups in the molecule, i.e., a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, i.e., a polyfunctional oxetane compound, a plurality of compounds in the molecule Examples thereof include compounds having a thioether group, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, NC-3000, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd., A.C. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (All trade names) bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; jER604, Etoto YH-434 manufactured by Tohto Kasei Co., Ltd., Sumitomo Chemical Co., Ltd. Sumi-epoxy ELM-120, etc. (all trade names) glycidylamine type epoxy resin; Daicel Chemical Industries, Ltd. Celoxide 2021, etc. Product name) alicyclic epoxy resin; YL-933, DA made by Japan Epoxy Resin Co., Ltd. Chemical Co., Ltd. of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Japan Epoxy Resin YL-6056, YX-4000, YL-6121 (all trade names), etc. Bisphenol S type epoxy resins such as xylenol type or biphenol type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Industrial Co., Ltd., EXA-1514 manufactured by DIC Industrial Co., Ltd .; Mitsubishi Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Kagaku Co .; tetraphenylolethane type epoxy resin of jERYL-931 (trade name) manufactured by Mitsubishi Chemical; Araldide PT810 manufactured by BASF, Nissan Chemical Industries, Ltd. Heterocyclic products such as TEPIC made by the company (both trade names) Poxy resin; diglycidyl phthalate resin such as Bremer DGT manufactured by NOF Corporation; tetraglycidyl xylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, and EXA-4700; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; CP-50S and CP- manufactured by NOF Corporation Examples thereof include glycidyl methacrylate copolymer epoxy resins such as 50M; further copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.) and the like. Is not limited to these . Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bixylenol type epoxy resin or a mixture thereof is particularly preferable. These epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the episulfide resin having a plurality of cyclic thioether groups in the molecule include YL7000 (bisphenol A type episulfide resin) 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 having a plurality of cyclic (thio) ether groups in the molecule is such that the cyclic (thio) ether group is 0.6 to 1 equivalent to 1 equivalent of the carboxyl group of the carboxyl group-containing resin. An amount of 2.5 equivalents is preferred, and an amount of 0.8 to 2.0 equivalents is more preferred. When the amount is less than 0.6 equivalents, carboxyl groups may remain in the solder resist film, and heat resistance, alkali resistance, electrical insulation, and the like may decrease. On the other hand, when the amount exceeds 2.5 equivalents, a low molecular weight cyclic ( When the thio) ether group remains in the dry coating film, the strength of the coating film may be reduced.

  Moreover, in addition to the said thermosetting component, thermosetting components, such as amino resins, such as a melamine derivative and a benzoguanamine derivative, can be used for the curable resin composition of this invention. Examples of such thermosetting components include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, methylol urea compounds, alkoxymethylated melamine compounds, alkoxymethylated benzoguanamine compounds, alkoxymethylated glycoluril compounds, and alkoxymethylated ureas. Compound etc. are mentioned. The type of the alkoxymethyl group is not particularly limited, and for example, it can be 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. The said thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more type.

  Commercially available products of these thermosetting components include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202. 1156, 1158, 1123, 1170, 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, and the like (manufactured by Sanwa Chemical Co., Ltd.).

  The amount of thermosetting component such as amino resin such as melamine derivative or benzoguanamine derivative is preferably 0.3 to 1.5 equivalent with respect to 1 equivalent of carboxyl group of (A) carboxyl group-containing resin. More preferred is an amount of 0.5 to 1.0 equivalent.

(Thermosetting catalyst)
When using the thermosetting component which has a some cyclic | annular (thio) ether group in the said molecule | numerator, 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 and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, as long as it is a thermosetting catalyst for epoxy resins or oxetane compounds, or a catalyst that promotes the reaction of epoxy groups and / or oxetanyl groups with carboxyl groups, either alone or in combination of two or more. Can be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

(Compound having isocyanate group or blocked isocyanate group)
In addition, a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is added to the curable resin composition of the present invention in order to improve the curability of the composition and the toughness of the resulting cured film. Can do. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is a compound having a plurality of isocyanate groups in one molecule, that is, a polyisocyanate compound, or a plurality of blocked isocyanate groups in one molecule. The compound which has, ie, a blocked isocyanate compound, etc. are mentioned.

  As said polyisocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

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

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

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

The compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.
The compounding amount of the compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is preferably 1 to 100 parts by mass, more preferably 100 parts by mass of (A) carboxyl group-containing resin. 2 to 70 parts by mass. When the blending amount is less than 1 part by mass, sufficient toughness of the coating film may not be obtained. On the other hand, when it exceeds 100 mass parts, storage stability may fall.

(Urethane catalyst)
A urethanization catalyst can be added to the curable resin composition of the present invention in order to accelerate the curing reaction of hydroxyl groups, carboxyl groups, and isocyanate groups. As the urethanization catalyst, it is preferable to use one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and amine salts.

  Examples of the tin catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

  The metal chloride is a metal chloride composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include cobalt chloride, ferrous nickel chloride, and ferric chloride.

  The metal acetylacetonate salt is a metal acetylacetonate salt made of Cr, Mn, Co, Ni, Fe, Cu or Al, for example, cobalt acetylacetonate, nickel acetylacetonate, iron acetylacetonate, etc. Is mentioned.

  The metal sulfate is a metal sulfate composed of Cr, Mn, Co, Ni, Fe, Cu, or Al, and examples thereof include copper sulfate.

  Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′. , N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl -N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1 -(2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imida 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′- Aminopropyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxy) Ethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, Examples thereof include N'-bis (2-hydroxypropyl) amine, melamine and / or benzoguanamine.

  Examples of the amine salt include an organic acid salt amine salt of DBU (1,8-diaza-bicyclo [5.4.0] undecene-7).

  The blending amount of the urethanization catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

(Photopolymerization initiator)
The curable resin composition of the present invention preferably contains a photopolymerization initiator. As the photopolymerization initiator, any known photopolymerization initiator can be used. Among them, an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, among others. Initiators are preferred. A photoinitiator may be used individually by 1 type and may use 2 or more types together.

  Examples of commercially available oxime ester photopolymerization initiators include CGI-325 manufactured by BASF, Irgacure (registered trademark) OXE01, Irgacure OXE02, N-1919 manufactured by Adeka, and Adeka Arcles (registered trademark) NCI-831. Is mentioned.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０又は１の整数である） In addition, a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used. Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula (I). .

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

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

  The amount of the oxime ester photopolymerization initiator used is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. If it is less than 0.01 part by mass, the photocurability on copper is insufficient, the coating film peels off, and the coating properties such as chemical resistance may be deteriorated. On the other hand, when it exceeds 5 parts by mass, light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5-3 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin.

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

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucillin (registered trademark) TPO and Irgacure 819 manufactured by BASF.

  Each compounding amount in the case of using an α-aminoacetophenone photopolymerization initiator or an acylphosphine oxide photopolymerization initiator is 0.01 to 15 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. Preferably there is. If the amount is less than 0.01 parts by mass, the photocurability on copper is similarly insufficient, the coating film peels off, and the coating properties such as chemical resistance may deteriorate. On the other hand, if it exceeds 15 parts by mass, a sufficient effect of reducing the outgas cannot be obtained, and light absorption on the surface of the solder resist coating film becomes violent, and the deep curability tends to decrease. More preferably, it is 0.5-10 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin.

In particular, the curable resin composition of the present invention preferably uses an oxime ester photopolymerization initiator. The effect is that not only a sufficient sensitivity can be obtained even in a small amount, but also the shrinkage of the cured coating film can be suppressed because the volatilization of the photopolymerization initiator in the post-heating process at the time of thermosetting and mounting is small Therefore, it is possible to greatly reduce the warpage.
In addition, the use of an acylphosphine oxide-based photopolymerization initiator improves the deep curability during photoreaction, and further incorporates an initiator-derived phosphorus-containing compound component cleaved by light irradiation into the cured product network, thereby allowing the cured coating to be cured. The phosphorus concentration in the film can be effectively increased, and the flame retardancy of the resulting cured product can be improved.

  In the curable resin composition of the present invention, it is effective to use either an oxime ester photopolymerization initiator or an acylphosphine oxide photopolymerization initiator, but the balance of the resist line shape and opening as described above is effective. From the standpoints of improving processing accuracy, and further improving low warpage, bendability, and flame retardancy, the combined use of an oxime ester photopolymerization initiator and an acylphosphine oxide photopolymerization initiator is more preferable.

(Photoinitiator or sensitizer)
(B) In addition to the photopolymerization initiator, a photoinitiator aid or a sensitizer can be suitably used for the curable resin composition of the present invention. Examples of the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds. These compounds may be used as (B) a photopolymerization initiator, but are preferably used in combination with (B) a photopolymerization initiator. Moreover, a photoinitiator auxiliary or a sensitizer may be used individually by 1 type, and may use 2 or more types together.

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

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

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

  Examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like.

  Examples of the ketal compound include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Examples of the benzophenone compound include benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4′-methyl diphenyl sulfide, 4-benzoyl-4′-ethyl diphenyl sulfide, 4-benzoyl-4′-propyl diphenyl sulfide, and the like. .

Examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nissoure (registered trademark) MABP manufactured by Nippon Soda Co., Ltd.), 4 , 4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.) and the like, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methyl Coumarin compounds such as coumarin), ethyl 4-dimethylaminobenzoate (Nippon Kayaku Co., Ltd. Kayacure (registered trademark) EPA), ethyl 2-dimethylaminobenzoate (Quantacure DMB manufactured by International Bio-Synthetics) ) 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamylethyl ester (Nippon Kayaku Co., Ltd. Kayacure DMBI), 4-dimethylamino Examples include 2-ethylhexyl benzoate (Esolol 507 manufactured by VanDyk). As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, and ketocoumarins are particularly preferable.
As the dialkylaminobenzophenone compound, 4,4′-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored, and use colored pigments as well as colorless and transparent photosensitive compositions, and colors that reflect the color of the colored pigments themselves It becomes possible to obtain a solder resist film. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, by including a thioxanthone compound, it is possible to improve deep curability.

  As a compounding quantity when using a photoinitiator adjuvant or a sensitizer, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin. When the blending amount of the photoinitiator assistant or sensitizer is less than 0.1 parts by mass, a sufficient sensitizing effect tends to be not obtained. On the other hand, when the amount exceeds 20 parts by mass, light absorption on the surface of the coating film by the tertiary amine compound becomes violent, and the deep curability tends to decrease. More preferably, it is 0.1-10 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin.

  The total amount of the photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 parts by mass, the deep curability tends to decrease due to light absorption.

  In addition, since these photopolymerization initiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, in some cases, the sensitivity is lowered, and the photopolymerization initiator, the photoinitiator assistant, and the sensitizer may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

(Compound having an ethylenically unsaturated group (photosensitive monomer))
The curable resin composition of the present invention may use a compound (photosensitive monomer) having one or more ethylenically unsaturated groups in the molecule. A compound having one or more ethylenically unsaturated groups in the molecule is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the carboxyl group-containing resin in an alkaline aqueous solution.

  Examples of the compound used as the photosensitive monomer include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. . Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like; Multivalent acrylates such as a peroxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct; a polyvalent such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adduct or propylene oxide adduct of these phenols Acrylates: glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, Polyacrylate polyol and other polyols are directly acrylated or urethane acrylated via diisocyanate Acrylates and melamine acrylates and / or methacrylates corresponding to the above acrylates.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound obtained by reacting a half urethane compound may be used as a photosensitive monomer. Such an epoxy acrylate resin can improve curability without deteriorating the touch drying property.

  In particular, in the present invention, polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts, and polyphenols such as ethylene oxide adducts or propylene oxide adducts of phenols. Valent acrylates and further (meth) acrylate-containing urethane oligomers can be suitably used from the viewpoint of low warpage and bendability.

  The compounding amount of the compound having a plurality of ethylenically unsaturated groups in the molecule used as the photosensitive monomer is preferably 5 to 100 parts by mass, more preferably 100 parts by mass of the (A) carboxyl group-containing resin. Is a ratio of 5 to 70 parts by mass. When the blending amount is less than 5 parts by mass, curability is lowered, and pattern formation may be difficult due to alkali development after irradiation with active energy rays. On the other hand, when it exceeds 100 mass parts, the solubility with respect to alkaline aqueous solution may fall, and a coating film may become weak.

(Coloring agent)
In the present invention, a colorant can be used. As the colorant to be used, conventionally known colorants such as red, blue, green, yellow, and white can be used, and any of pigments, dyes, and pigments may be used. As a specific example, the following color index (CI; issued by The Society of Dyers and Colorists) numbers can be given. 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: PigmentRed 171, Pigment Red 175, PigmentRed 176, Pigment Red 185, PigmentRed 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: PigmentRed 254, Pigment Red 255, PigmentRed 264, Pigment Red 270, PigmentRed 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 Red168, Pigment Red 177, Pigment Red216, Solvent Red 149, Solvent Red150, Solvent Red 52, Solvent Red207.
Kinacridone series: Pigment Red122, Pigment Red 202, Pigment Red206, Pigment Red 207, Pigment Red209.

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.
As the dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70, etc. are used. be able to. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, green colorants include phthalocyanine, anthraquinone, and perylene. 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: SolventYellow 163, Pigment Yellow 24, PigmentYellow 108, Pigment Yellow 193, PigmentYellow 147, Pigment Yellow 199, PigmentYellow 202.
Isoindolinone series: PigmentYellow 110, Pigment Yellow 109, PigmentYellow 139, Pigment Yellow 179, PigmentYellow 185.
Condensed azo series: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 112.
Benzimidazolone series: PigmentYellow 120, Pigment Yellow 151, PigmentYellow 154, Pigment Yellow 156, PigmentYellow 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 series: 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, PigmentViolet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black And the like.

  The blending amount of the colorant is not particularly limited, but is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). .

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。 (Phosphorus-containing compound)
The curable resin composition of the present invention preferably contains a phosphorus-containing compound. As the phosphorus-containing compound, conventionally known compounds can be used as organic phosphorus flame retardants. Among these, phosphate esters and condensed phosphate esters, cyclic phosphazene compounds, phosphazene oligomers, phosphinic acid metal salts, or compounds represented by the following general formula (II) are preferable. Moreover, what has an acrylate group as a reactive group (phosphorus element containing (meth) acrylate), what has a phenolic hydroxyl group, an oligomer or a polymer, a phosphazene oligomer, and a phosphinate can also be used suitably.

In the formula, R ¹ , R ² and R ³ each independently represent a substituent other than a halogen atom.

  Examples of commercially available phosphorus-containing compounds represented by the general formula (II) include HCA, SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sanko Co., Ltd.), and the like.

The phosphorus element-containing (meth) acrylate is preferably a compound having a phosphorus element and having a plurality of (meth) acryloyl groups in the molecule, specifically, R ¹ in the general formula (II) and Examples include compounds in which R ² is a hydrogen atom and R ³ is a (meth) acrylate derivative. Generally, it can be synthesized by a Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a known and commonly used polyfunctional (meth) acrylate monomer.

  Examples of the known and commonly used (meth) acrylate monomers include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tris-hydroxy. Polyhydric alcohols such as ethyl isocyanurate or polyethyl acrylates such as these ethylene oxide adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts of these phenols or Polyhydric acrylates such as propylene oxide adducts; and urethane acrylates of the above polyalcohols, Examples include polyvalent acrylates of glycidyl ethers such as glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and melamine acrylate and / or methacrylates corresponding to the acrylate. .

  The phosphorus-containing compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, does not deteriorate electrical characteristics due to hydrolysis, and has high solder heat resistance. Further, as an appropriate combination, when an epoxy resin is used among thermosetting resins, there is an advantage that it does not bleed out after curing because it reacts with the epoxy group and is taken into the network. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.

  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 bleedout after curing due to 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.

  As the phosphazene oligomer, a phenoxyphosphazene compound is effective, and there are a substituted or unsubstituted phenoxyphosphazene oligomer or a trimer, a tetramer, and a pentamer, and there are liquid and solid powders. It can be preferably used. Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd. Among these, a phenoxyphosphazene oligomer substituted with an alkyl group or a polar group such as a hydroxyl group or a cyano group is preferable because it has high solubility in a carboxyl group-containing resin and does not cause problems such as recrystallization even when added in a large amount.

  By using a phosphinic acid metal salt, flame retardancy can be improved without impairing the flexibility of the cured coating film. In addition, by using a phosphinic acid metal salt that is excellent in heat resistance, the bleedout of the flame retardant can be suppressed in the hot press during mounting. Commercially available products include EXOLIT OP 930, EXOLIT OP 935 and the like manufactured by Clariant.

  The amount of the phosphorus-containing compound as a flame retardant is preferably in the range of 1 to 200 parts by mass, particularly preferably 5 to 100 parts by mass, with respect to 100 parts by mass of the (A) carboxyl group-containing resin. If it exceeds 200 parts by mass, the resulting cured film may be undesirably deteriorated in heat resistance, bending characteristics and the like.

(Other fillers (fillers))
The curable resin composition of the present invention may be blended with other fillers (fillers) in order to increase the physical strength of the coating film or cured product, or to improve the concealability of the cured product. As such a filler, known inorganic or organic fillers can be used, and Neuburg silica particles, barium sulfate, spherical silica and talc are particularly preferable. Among these, Neuburg silica particles have a refractive index close to that of resins, and even when filled high, the resolution of the solder resist is not deteriorated and the linear expansion coefficient can be reduced. In addition, this Neuburg silica particle refers to what is not baked. Furthermore, in order to obtain a white appearance and flame retardancy, metal hydroxides, metal hydroxides such as aluminum hydroxide, and boehmite can also be used as fillers. Moreover, sufficient wettability with respect to resins can be obtained by adding a silane coupling agent to other fillers. 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 .

  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 (A) carboxyl group-containing resin. Part. When the compounding quantity of a filler exceeds 500 mass parts, the viscosity of curable resin composition may become high and printability may fall, or hardened | cured material may become weak.

(Binder polymer)
In the curable resin composition of the present invention, a conventionally known binder polymer can be used for the purpose of flexibility and dryness to touch. As the binder polymer, cellulose-based, polyester-based, phenoxy resin-based, and polymers are preferable. As cellulose-based, cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd. can be mentioned. As the Byron series and phenoxy resin systems manufactured by the company, phenoxy resins of bisphenol A, bisphenol F and their hydrogenated compounds are preferred.

  The addition amount in the case of using the binder polymer 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 (A) carboxyl group-containing resin. It is. When the compounding quantity of a binder polymer exceeds 50 mass parts, the alkali developability of curable resin composition is inferior, and the pot life which can be developed may become short.

(Elastomer)
The curable resin composition of the present invention can use an elastomer for the purpose of imparting flexibility and improving the brittleness of the cured product. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyesteramide elastomer, an acrylic elastomer, or an olefin elastomer can be used. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. These elastomers may be used alone or in combination of two or more.

(Adhesion promoter)
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. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade name: Accel M from Kawaguchi Chemical Industry Co., Ltd.), 3 -Morpholinomethyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, Amino group-containing benzotriazole, silane coupling agent and the like can be mentioned.

(Antioxidant)
In order to prevent oxidation, the curable resin composition of the present invention decomposes the generated radical scavenger and the generated peroxide into harmless substances so as not to generate new radicals. Antioxidants such as peroxide decomposers can be included. The antioxidant used in the present invention can prevent oxidative deterioration of a carboxyl group-containing resin or the like and suppress yellowing. In addition to the effects described above, the addition of an antioxidant improves the process margin for producing the curable resin composition, such as prevention of halation due to the photocuring reaction of the curable resin composition and stabilization of the opening shape. It becomes possible. An antioxidant may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the antioxidant acting 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)- Phenol compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-tetrame -4-piperidyl) - sebacate, and the like amine compounds such as phenothiazine. Examples of commercially available products include 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 (and above, ADEKA). IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 (trade name, manufactured by BASF).

  Examples of the antioxidant acting as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3′-thiodipro Sulfur compounds such as pionate can be mentioned. Examples of commercially available products include ADK STAB TPP (trade name, manufactured by ADEKA), Mark AO-412S (trade name, manufactured by Adeka Argus Chemical Co., Ltd.), and Sumilizer TPS (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

  0.01 mass part-10 mass parts are preferable with respect to 100 mass parts of (A) carboxyl group-containing resin, when using the said antioxidant, 0.01-5 mass parts is more preferable. When the blending amount of the antioxidant is less than 0.01 parts by mass, the effect of adding the antioxidant may not be obtained. On the other hand, blending in a large amount exceeding 10 parts by mass is not preferred because there is a risk of inhibition of photoreaction, poor development with respect to an alkaline aqueous solution, deterioration of tackiness, and deterioration of coating film properties.

  In addition, the above-mentioned antioxidants, particularly phenolic antioxidants, may exhibit further effects when used in combination with a heat stabilizer, so a heat stabilizer is added to the curable resin composition of the present invention. May be.

  Examples of the heat stabilizer include phosphorus, hydroxylamine, and sulfur heat stabilizers. Examples of commercially available products of these heat stabilizers, IRGAFOX168, IRGAFOX12, IRGAFOX38, IRGASTAB PUR68, IRGASTAB PVC76, IRGASTAB FS301FF, IRGASTAB FS110, IRGASTAB FS210FF, IRGASTAB FS410FF, IRGANOX PS800FD, IRGANOX PS802FD, RECYCLOSTAB 411, RECYCLOSTAB 451AR, RECYCLOSSORB 550, RECYCLOBLEND 660 (above, manufactured by BASF, trade name). The said heat stabilizer may be used individually by 1 type, and may use 2 or more types together.

  The blending amount in the case of using the heat stabilizer is preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

(UV absorber)
In general, the polymer material absorbs light and thereby decomposes and deteriorates. Therefore, the curable resin composition of the present invention includes, in addition to the above-mentioned 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.

Examples of commercially available ultraviolet absorbers include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479, and more. BASF, trade name) and the like.
Said ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type. By using together with the antioxidant, the molded product obtained from the curable resin composition of the present invention can be stabilized.

(Organic solvent)
Furthermore, the curable resin composition of the present invention can use an organic solvent for the synthesis of the carboxyl group-containing resin and the adjustment of the composition, or for the adjustment of the viscosity for application to a substrate or a carrier film. .
Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

(Chain transfer agent)
In the curable resin composition of the present invention, known and commonly used N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as a chain transfer agent in order to improve sensitivity. Examples of chain transfer agents include 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, mercaptopropanediol Chain transfer agents having a hydroxyl group such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2,2- (ethylenediene), mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; Oxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclopentanthi Lumpur, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

A polyfunctional mercaptan-based compound can also be used as a chain transfer agent. Examples of the polyfunctional mercaptan compound include aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide, xylylene dimercaptan, 4,4. Aromatic thiols such as' -dimercaptodiphenyl sulfide, 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate) , Trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), dipen Poly (mercaptoacetate) polyhydric alcohols such as erythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate), propylene glycol bis (3- Mercaptopropionate), glycerol tris (3-mercaptopropionate), trimethylol ethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate) And poly (3-mercaptopropionate) of polyhydric alcohols such as dipentaerythritol hexakis (3-mercaptopropionate); 1,4-bis (3-mercaptobutyryl) Oxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3- And poly (mercaptobutyrate) s such as mercaptobutyrate).
Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, And Karenz-NR1 (manufactured by Showa Denko KK).

  Moreover, the heterocyclic compound which has a mercapto group as a chain transfer agent can also be used. Examples of the heterocyclic compound having a mercapto group 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-valerolactone, 2-mercap -5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto-5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2,4,6- Trimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name Disnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd .: trade name Disnet DB), and 2 -Anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: DYSNET AF) That.

  In particular, since the developability of the curable resin composition is not impaired, mercaptobenzothiazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4- Thiadiazole-2-thiol, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These chain transfer agents may be used individually by 1 type, and may use 2 or more types together.

(Additive)
If necessary, the curable resin composition of the present invention may further contain a thixotropic agent such as finely divided silica, organic bentonite, montmorillonite, hydrotalcite and the like. As the thixotropic agent, organic bentonite and hydrotalcite are preferable because of excellent stability over time, and hydrotalcite is particularly preferable because of excellent electrical characteristics. Also, thermal polymerization inhibitors, antifoaming agents and / or leveling agents such as silicones, fluorines and polymers, rust inhibitors, and copper damage inhibitors such as bisphenols and triazine thiols Known and commonly used additives 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.

(Dry film)
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, a peelable cover film is preferably laminated on the film surface for the purpose of preventing dust from adhering to the film surface.
As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film 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, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the carboxyl group of the (A) carboxyl group-containing resin and the thermosetting component React to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. Even if it does not contain a thermosetting component, the ethylenically unsaturated bond remaining in an unreacted state at the time of exposure undergoes thermal radical polymerization even when it does not contain a thermosetting component, thereby improving the coating film properties. Thus, 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 also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 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 The present invention will be specifically described below 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 (13))
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introducing tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy 2-ethylhexanoate (Nippon Yushi) as a polymerization initiator 21.4 g of Perbutyl O manufactured by Co., Ltd. was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Daicel Chemical Industries, Ltd., Plaxel FM1) were added to the bis ( 4-t-butylcyclohexyl) peroxydicarbonate (Perroyl TCP manufactured by Nippon Oil & Fats Co., Ltd.) was added dropwise over 3 hours, and further aged for 6 hours to obtain a carboxyl group-containing copolymer resin. It was. The reaction was performed under a nitrogen atmosphere.
Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Daicel Chemical Co., Ltd. Cyclomer A200), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, polymerization inhibition were added to the obtained carboxyl group-containing copolymer resin. As an agent, 1.80 g of hydroquinone monomethyl ether was added, heated to 100 ° C., and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a solution containing 53.8% by weight (nonvolatile content) of a carboxyl group-containing resin having a solid content acid value of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained. Hereinafter, this is referred to as varnish A-1.

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

[Synthesis Example 3]
(A-3: 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. Hereinafter, this is referred to as varnish A-3.

(A-4: Synthesis of a resin corresponding to the carboxyl group-containing resin (7))
Orthoethylene glycol novolak type epoxy resin (DIC Corporation, EPICLON (registered trademark) N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups) (diethylene glycol monoethyl ether acetate 600 g) Total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100 ° C. to uniformly dissolve.
Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. To the obtained reaction liquid, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were charged, reacted at 110 ° C. for 4 hours, and cooled.
Thus, a resin solution having a solid content acid value of 89 mgKOH / g and a solid content of 65% was obtained. Hereinafter, this is referred to as varnish A-4.

(Examples 1-12, Comparative Examples 1-3)
Using the resin solutions (varnishes A-1 to A-4) of the respective synthesis examples, blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, and premixed with a stirrer, The mixture was kneaded with a three-roll mill to prepare a curable resin composition for solder resist. Here, it was 15 micrometers or less when the dispersion degree of the obtained curable resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

＊１：ＣＲ９７、石原産業株式会社製
＊２：サテントン５、ＢＡＳＦ社製
＊３：ＳＴ−２０００、日本タルク（株）製
＊４：シルフィットＺ９１、ホフマンミネラル社製
＊５：ＮＣ−３０００−Ｈ−ＣＡ７５、日本化薬社製ビフェニルノボラック型エポキシ樹脂のカルビトールアセテート溶液（固形分７５％）
＊６：ＴＰＡ−Ｂ８０Ｅ、旭化成ケミカルズ（株）社製ブロックイソシアネート
＊７：ルシリンＴＰＯ、ＢＡＳＦ社製アシルホスフィンオキサイド系光重合開始剤
＊８：イルガキュア８１９、ＢＡＳＦ社製アシルホスフィンオキサイド系光重合開始剤
＊９：アデカアークルズ ＮＣＩ−８３１、（株）ＡＤＥＫＡ社製光重合開始剤
＊１０：イルガキュアＯＸＥ−０２ＢＡＳＦ社製オキシムエステル系光重合開始剤
＊１１：Ｍ−３５０、東亜合成（株）製トリメチロールプロパンＥＯ変性トリアクリレート
＊１２：ＳＰＥ−１００、大塚化学（株）製
＊１３：エクソリットＯＰ９３５Ｅ、クラリアント社製
＊１４：ＨＦＡ−６００７Ｅ、昭和電工（株）社製
＊１５：イルガノックス１０１０、ＢＡＳＦ社製

* 1: CR97, manufactured by Ishihara Sangyo Co., Ltd. * 2: Satinton 5, manufactured by BASF * 3: ST-2000, manufactured by Nippon Talc Co., Ltd. * 4: Sylfit Z91, manufactured by Hoffman Mineral * 5: NC-3000- H-CA75, a carbitol acetate solution of biphenyl novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd. (solid content: 75%)
* 6: TPA-B80E, block isocyanate manufactured by Asahi Kasei Chemicals Corporation * 7: Lucirin TPO, acylphosphine oxide photopolymerization initiator manufactured by BASF * 8: Irgacure 819, acylphosphine oxide photopolymerization initiator manufactured by BASF * 9: Adeka Arcles NCI-831, photopolymerization initiator manufactured by ADEKA Corporation * 10: Oxime ester photopolymerization initiator manufactured by Irgacure OXE-02BASF * 11: M-350, manufactured by Toagosei Co., Ltd. Methylolpropane EO-modified triacrylate * 12: SPE-100, manufactured by Otsuka Chemical Co., Ltd. * 13: Exorit OP935E, manufactured by Clariant Co., Ltd. * 14: HFA-6007E, manufactured by Showa Denko Co., Ltd. * 15: Irganox 1010, BASF Made by company

Performance evaluation:
<Optimum exposure amount>
The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3 were coated on the entire surface by a screen printing method after washing a circuit pattern substrate with a copper thickness of 35 μm after buffing, washing with water, and drying, and then applying 80 ° C. For 30 minutes in a hot air circulation drying oven. 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 carried out in 60 seconds was 6 steps, the optimum exposure amount was set.

<Resolution evaluation>
The front surfaces of the curable resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3 were applied onto a copper flat substrate by screen printing and dried at 80 ° C. for 30 minutes (dry film thickness of about 40 μm). A negative film having L / S (line / space) = 100/500 μm and L / S (line / space) = 80/500 μm was exposed at an optimum exposure amount, and developed under the above conditions. After development, it was checked whether 100 μm and 80 μm lines remained, and evaluation was performed as follows.
○: An 80 μm line remains on the copper solid substrate.
Δ: A 100 μm line remains on the copper solid substrate.
X: A 100-micrometer line does not remain on a copper solid board | substrate.

Characteristic evaluation substrate manufacturing procedure:
The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3 were applied onto the patterned copper foil substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature ( Dry film thickness of about 20 μm). The obtained substrate is exposed to a solder resist pattern at an optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed at a pressure of 0.2 MPa. Was developed for 60 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes.
The curable resin composition of Example 12 of the previous period was cured by heating at 150 ° C. for 60 minutes after pattern printing on a copper foil substrate. The characteristics of the obtained printed circuit board (evaluation board) were evaluated as follows.

<Electroless gold plating resistance>
Using commercially available electroless nickel plating bath and electroless gold plating bath, plating was performed under the conditions of nickel 3 μm and gold 0.03 μm, and after evaluating the presence or absence of peeling of the resist layer or the presence of plating penetration, The presence or absence of peeling of the resist layer was evaluated by tape peeling. The judgment criteria are as follows.
○: Infiltration and peeling are not seen.
Δ: Slight penetration is observed after plating, but does not peel off after tape peeling.
X: There is peeling after plating.

<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 observed after immersion for 10 seconds. X: Resist layer swelled and separated after immersion for 10 seconds.

<Whiteness>
The whiteness of the obtained substrate on the solder resist was measured with a Minolta color difference meter CR-400 and evaluated according to the following criteria.
○: Y value is 75 or more Δ: Y value is 70 or more and less than 75 ×: Y value is less than 70

<Flame retardance>
The curable resin compositions of Examples and Comparative Examples were applied to the entire surface of 0.2 mm and 0.4 mm thick FR-4 substrates by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 20 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. The curable resin compositions of Examples 1 to 11 and Comparative Examples 1 to 3 were coated on the entire surface of the solder resist with the optimum exposure amount using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp. The sample was exposed to light, developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds, and thermally cured at 150 ° C. for 60 minutes to obtain an evaluation sample.
The curable resin composition of Example 12 was cured by heating the obtained double-sided coated substrate at 150 ° C. for 60 minutes. This flame retardant evaluation sample was subjected to a vertical combustion test based on the UL94 standard. Evaluation was expressed as V-0 or V-1 based on the UL94 standard. The results of each evaluation test are summarized in Table 2.

(Examples 13 to 15)
A curable resin composition prepared by adding the curable resin composition shown in Tables 6 to 8 shown in Table 1 without blending a silicone-based antifoaming agent was diluted with methyl ethyl ketone, applied onto a carrier film, and dried by heating. Then, a photosensitive resin composition layer having a thickness of 20 μm was formed, and a cover film was bonded 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 dry film having the composition of Example 6 corresponds to Example 13, the composition of Example 7 corresponds to Example 14, and the composition of Example 8 corresponds to Example 15. The results are described below.

From the results shown in Tables 2 and 3, in the case of the resin composition of Example 1, a cured product having sufficient resolution, electroless gold plating resistance, solder heat resistance, and whiteness can be obtained. It was. Moreover, in the case of the flame-retardant resin composition of Examples 2-11, it has sufficient resolution, electroless gold plating resistance, solder heat resistance, whiteness, and also has excellent flame retardancy. A cured product could be obtained. This is thought to be because the use of a filler obtained by calcining a hydrous silicate mineral containing aluminum or magnesium improved the light transmittance and sufficiently improved the flame retardancy to the depth.
On the other hand, in the case of Comparative Examples 1 and 2 that do not contain a filler obtained by firing a hydrous silicate mineral containing aluminum or magnesium, it is found that it is difficult to obtain a cured product having sufficient resolution and flame retardancy. . Further, in the case of the resin composition of Comparative Example 3 containing no titanium oxide, the obtained cured product was excellent in resolution and flame retardancy, but the whiteness was insufficient.

Claims (8)

A white curable resin composition comprising a filler obtained by firing a hydrated silicate mineral containing (A) a carboxyl group-containing resin, (B) titanium oxide, and (C) aluminum or magnesium. Furthermore, the white curable resin composition of Claim 1 containing a thermosetting component. Furthermore, the white curable resin composition of Claim 1 or 2 containing a photoinitiator and a photosensitive monomer. The white curable resin composition according to any one of claims 1 to 3, wherein the filler obtained by firing the hydrous silicate mineral containing (C) aluminum or magnesium is fired Neuburg silica particles. It is a solder resist, The white curable resin composition as described in any one of Claims 1-4. A dry film obtained by applying and drying the white curable resin composition according to any one of claims 1 to 5 on a film. A cured film obtained by heat-curing and / or photocuring the white curable resin composition according to any one of claims 1 to 5 or the dry film according to claim 6.   A printed wiring board comprising the cured film according to claim 7.