WO2002096969A1

WO2002096969A1 - Light- and heat-curing resin composition

Info

Publication number: WO2002096969A1
Application number: PCT/JP2002/004955
Authority: WO
Inventors: Teruo Saito
Original assignee: Taiyo Ink Manufacturing Co., Ltd.
Priority date: 2001-05-25
Filing date: 2002-05-22
Publication date: 2002-12-05
Also published as: TWI242021B; JP4309246B2; JPWO2002096969A1

Abstract

A light- and heat-curing resin composition comprising (A) a resin compound which bears in the molecule both two or more (meth)acryloyl groups and a carboxyl group and has a weight-average molecular weight of 2,000 to 40,000 and an acid value of 50 to 250 mgKOH/g, (B) a compound which bears in the molecule both two or more (meth)acryloyl groups and a carboxyl group and has a weight-average molecular weight of 300 to 1,500, (C) a photo-radical polymerization initiator, and (D) an epoxy resin. This resin composition is useful as solder resist in the production of printed wiring boards, or suitable for the formation of insulating interlayers of printed wiring boards by a build-up process.

Description

Specification

Photocurable and thermosetting resin composition

The present invention relates to a photocurable / thermosetting resin composition suitable for forming various resin adhesive layers, a solder resist for manufacturing a printed wiring board, an intermediate insulating layer of a printed wiring board by a build-up method, and the like. More specifically, it is highly sensitive to UV exposure, has good developability with alkaline aqueous solution, and has chemical resistance such as electroless plating resistance, mechanical properties, heat resistance, and electrical insulation. The present invention relates to a photo-curing / thermo-curing resin composition capable of forming a cured film excellent in properties and the like, and a printed wiring board using the same. Background art

With the rapid progress of recent semiconductor components, electronic devices tend to be smaller and lighter, have higher performance, and have more functions. Following these trends, the density of printed wiring boards has been increasing. Conventionally, a solder resist used for such a printed wiring board is formed by patterning a thermosetting composition or a photocurable composition by screen printing, and then thermosetting or photocuring the transfer portion. Generally, development-type solder-resist as disclosed in Japanese Patent Publication No. 61-243 46969 is becoming mainstream in response to the increasing density of printed wiring boards. .

Such a development-type solder resist is coated on a printed wiring board by a screen printing method, a curtain coating method, a spray coating method, a roll coating method, or the like. It requires a temporary drying step to volatilize, an exposure step to cool and contact exposure, a development step to remove unexposed areas by development, and a heat curing step to obtain sufficient coating film properties. Of these processes, the exposure process is an extremely complicated process such as exchanging a negative film depending on the type of printed wiring board, performing alignment, evacuating, and exposing. Therefore, shortening the exposure process is a major factor in improving productivity and reducing costs, and solder resist is a key factor in shortening the exposure process. High sensitivity contributes greatly. For these reasons, there is a growing demand for higher sensitivity solder resists used in general-purpose electronic devices. In general, it is conceivable to add a large amount of a polyfunctional (meth) acrylate compound to increase the sensitivity. However, when the amount of the low molecular weight polyfunctional (meth) acrylate compound is increased, the sensitivity is increased, but the touch dryness (tack-free property) required during contact exposure is significantly reduced, and the properties of the cured coating film are also reduced. There is a problem. On the other hand, the manufacture of printed wiring boards used for small-volume production models such as analytical instruments, and the manufacture of prototype printed wiring boards, are directly performed by CAD (Computer Aided Design) data from a computer. There is a demand for a solder resist that is compatible with laser, direct, and imaging methods for drawing images with a laser. The laser beam used for such laser direct imaging has a beam diameter of 5 to 15 and an output of several watts. Scanning with a width of 5 to 15 m while turning on and off such a laser beam, and drawing an image, the time required to form a pattern on a single printed wiring board depends on the sensitivity of the solder register. Greatly depends on For these reasons, a laser-direct imaging solder resist is required to have higher sensitivity than a development-type solder resist by general-purpose contact exposure.

In addition, the increase in the density of printed wiring boards tends to reduce the area of the connection portion and reduce the connection reliability. For this reason, it is necessary to make it difficult for the connecting portion to be oxidized by electroless gold plating or the like. Such electroless plating is performed by dipping in a high-temperature or acidic plating bath for a relatively long time, so that a solder resist is required to have high chemical resistance. Furthermore, in the electroless gold plating, the deposited metal particles gradually become larger, so that the stress that spreads the solder resist to the side works and the phenomenon that the solder resist around the electroless gold plating peels off easily occurs. Become. The peeling of the solder resist due to such electroless gold plating largely depends on the adhesion between the solder resist and the copper foil and the refractivity of the solder resist. Generally, when the amount of the polyfunctional (meth) acrylate compound is increased in order to increase the photocurability, the elasticity of the cured coating film increases, and the resistance to electroless gold plating decreases. Furthermore, in the case of solder resists for printed wiring boards, the thickness of the solder resist between IC and LSI connection terminals (pads) tends to be greater than that on copper foil. Thus, the solder resist is different from the etching resist and the like, and it is necessary to obtain stable resolution even with coating films having different thicknesses. Naturally, high solder heat resistance is also required. However, if a large amount of aromatic resin is used to obtain heat resistance, the internal curing of the solder resist during exposure is reduced due to light absorption by the resin itself, and the resolution during formation of a thick film is reduced. There is a problem of decline.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and its basic purpose is to reduce the characteristics of a cured coating film and to enable contact exposure of a dried coating film. An object of the present invention is to provide a photo-curable / thermo-curable resin composition having sufficient dryness to the touch and high photocurability with high sensitivity.

Further, an object of the present invention is to provide a photocurable and thermosetting resin which has stable resolution even when the film thickness of the coating film changes, and which does not cause peeling of the cured coating film during electroless plating. It is to provide a composition.

Another object of the present invention is to provide a printed wiring board having an interlayer insulating layer and / or a solder resist layer formed from such a photocurable and thermosetting resin composition. Disclosure of the invention

In order to achieve the above object, according to the present invention, (A) a compound having two or more (meth) acryloyl groups in one molecule and having a carboxyl group and having a weight average molecular weight of 2,000 A resin compound having an acid value of 50 to 250 mg K 0 H / g; (B) one or more (meth) acryloyl groups in one molecule, and Photocuring and thermosetting characterized by containing a carboxyl group-containing compound having a weight average molecular weight of 300 to 1,500, (C) a photoradical polymerization initiator, and (D) an epoxy resin. A resin composition is provided. Here, the term “(meth) acryloyl group” is a general term for an acryloyl group and a methylacryloyl group, and the same applies to other similar expressions. In a preferred embodiment, as one embodiment of the resin compound (A), a resin (a-1) having two or more (meth) acryloyl groups and two or more carboxyl groups in one molecule includes: A resin obtained by reacting a bifunctional epoxy resin (a-2) having two epoxy groups in one molecule is used.

In another preferred embodiment of the resin compound (A), a (meth) acrylic acid (a-3) is reacted with a bifunctional epoxy resin (a-2) having two epoxy groups in one molecule. After the reaction, a resin obtained by reacting a tetrabasic acid anhydride (a-4) is used. More preferably, as the bifunctional epoxy resin (a-2) having two epoxy groups in one molecule, a hydrogenated product of bisphenol A diglycidyl ether or bisphenol F diglycidyl ether is used. As the tetrabasic acid anhydride (a-4), an alicyclic tetrabasic acid anhydride is used.

Furthermore, as another preferred embodiment of the resin compound (A), a polyfunctional epoxy resin (a-5) represented by the following general formula (1) is reacted with (meth) acrylic acid (a-3). Then, a resin obtained by reacting polybasic acid anhydride (a-6) is used.

(1)

(In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or a glycidyl group, and n is a number of 39.)

Further, the compound (B) includes a compound (b-1) having one or more (meth) acryloyl groups and one or more alcoholic hydroxyl groups in one molecule, a polybasic acid anhydride (b — The compound obtained by reacting 2) is preferred. The compounding amount of the compound (B) is preferably 5100 parts by mass with respect to 100 parts by mass of the resin compound (A).

Further, as a preferred embodiment of the photoradical polymerization initiator, a compound represented by the following general formula (2) is used.

The photocurable and thermosetting resin composition of the present invention as described above is highly sensitive, has a stable resolution even when the film thickness of the coating film changes, and has the touch of a dry coating film. In addition to maintaining excellent properties such as dryness, heat resistance of the cured coating, and electrical insulation, the cured coating does not peel off during electroless plating.

Therefore, according to the present invention, there is further provided a printed wiring board having an interlayer insulating layer and / or a solder resist layer formed from the photocurable and thermosetting resin composition.

By using the photocurable and thermosetting resin composition of the present invention for forming the interlayer insulating layer and / or the solder resist layer of the printed wiring board, it becomes possible to shorten the exposure time, thereby improving productivity. And the cost of electronic equipment can be reduced. Furthermore, the use of laser direct imaging eliminates the need for a photo tool such as a negative film, shortens the time from design to commercialization, and makes it easier to produce prototypes. Best mode for carrying out the invention

As described above, the photo-curable and thermo-curable resin composition according to the present invention comprises, as a photo-curable component blended together with the photo-radical polymerization initiator (C) and the epoxy resin (D), Has two or more (meth) acryloyl groups and has a carboxyl group, has a weight average molecular weight of 2,000 to 4,000, and an acid value of 50 to 250 mg KOH / g in combination with resin compound (A) At least one, preferably two or more (meth) acryloyl groups, and a carboxyl group containing a compound (B) having a weight average molecular weight of 300 to 1,500. As a result, high sensitivity is achieved, and at the same time, the brittleness of the cured coating film is improved (the elastic modulus is improved), and peeling of the cured coating film during electroless gold plating is prevented. .

Conventionally used low-molecular-weight compounds having two or more (meth) acryloyl groups in one molecule to increase sensitivity have high density of photosensitive (meth) acryloyl groups and high photoreactivity. . However, since intramolecular polymerization occurs, it is difficult to increase the molecular weight, and the reaction product tends to be brittle. On the other hand, in the present invention, by introducing a thermosetting carboxyl group into a low molecular weight compound having a (meth) acryloyl group, a photocurable component which has not been polymerized by photocuring can be thermally crosslinked at the time of post cure. This improves the brittleness while increasing the molecular weight. If the weight-average molecular weight of the compound (B) is less than 300, the efficiency of increasing the molecular weight is low, and the boiling point is low, and the odor is undesirably increased. On the other hand, when the weight average molecular weight exceeds 1,500, the degree of freedom of the molecule is reduced, and the photocurability is undesirably reduced.

Hereinafter, each component of the photocurable and thermosetting resin composition of the present invention will be described in detail.

First, the above-mentioned one molecule has two or more (meth) acryloyl groups, and has a carboxyl group, a weight average molecular weight of 2,000 to 40,000, and an acid value of 500. As the resin compound (A) of up to 250 mg KOH / g, conventionally known various resin compounds can be used. In combination with the compound (B), the brittleness of the cured coating film is synergistically improved. In one embodiment suitable for (improving the elastic modulus), a resin (a-1) having two or more (meth) acryloyl groups and two or more carboxyl groups in one molecule includes: A resin obtained by reacting a bifunctional epoxy resin (a-2) having two epoxy groups in a molecule is used. Thus, a resin having two or more (meth) acryloyl groups and two or more carboxyl groups in one molecule via the bifunctional epoxy resin (a-2) By using a resin having a high molecular weight by linking (a-1), the brittleness of the cured coating film can be improved and the dryness of the dried coating film before development can be improved.

Examples of the resin (a-1) having two or more (meth) acryloyl groups and two or more carboxyl groups in one molecule include a phenol novolak type or a cresol novolak type epoxy resin. Carboxyl group-containing epoxy acrylates obtained by adding acrylic acid and then reacting with polybasic acid anhydride, and resins obtained by partially reacting acrylic acid copolymer resin with glycidyl methacrylate are used. .

On the other hand, the bifunctional epoxy resins (a-2) having two epoxy groups in one molecule to react with them include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and hydrogenated products thereof. , Bisphenol S diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Known bifunctional epoxy resins such as diol diglycidyl ether can be used, and they can be used alone or in combination of two or more.

Further, as another preferred embodiment of the resin compound (A), a bifunctional epoxy resin (a-2) having two epoxy groups in one molecule is provided with (meth) acrylic acid (a-3) And a resin obtained by reacting with tetrabasic acid anhydride (a-4). This resin becomes a linear high molecular weight resin and contributes to improving the brittleness of the cured coating film and improving the dryness of the dry coating film to the touch.

As the bifunctional epoxy resin (a-2) having two epoxy groups in one molecule, known and commonly used bifunctional epoxy resins as described above can be used, but bisphenol A diglycidyl ether (the above-mentioned general formula) By using a hydrogenated product of η = 0, RR ² = methyl group in (1) or bisphenol F diglycidyl ether (n = 0, R ² = H in the above general formula (1)), heat resistance can be improved. Increase the UV transmittance and reduce the In addition, thick film curability can be improved.

Examples of the tetrabasic acid anhydrides (a-4) include vilomeritic anhydride, benzophenonetetracarboxylic dianhydride, and biphenyl 3,4,3 ', 4'tetracarboxylic dianhydride. , Diphenyl ether- 3,4,3 ', 4'-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofurfuryl) _3-methyl-3-cyclohexene-1,2- Dicarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentenetetracarboxylic dianhydride, and the like. Cyclic 5- (2,5-dioxotetrahydrofurfuryl) 1,3-methyl-3-cyclohexene 1,2-dicarboxylic anhydride, 1,2,3,4-butanetracarboxylic dianhydride , 1,2,3,4-cyclopentene carboxylic acid dianhydride Without having to absorb, also free carboxylic acid produced when reacted with the alcoholic hydroxyl group is an aliphatic carboxylic acid, it becomes more soluble Al Chikarari solution, more preferable.

Further, as another preferred embodiment of the resin compound (A), (meth) acrylic acid (a-3) is added to a polyfunctional epoxy resin (a-5) represented by the following general formula (1). After the reaction, a resin obtained by reacting the polybasic acid anhydride (a-6) is exemplified.

(Wherein R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or a glycidyl group, and n is a number from 3 to 9.)

This resin has a low elastic modulus because the main skeleton is a linear polymer having n of 3 to 9 represented by the general formula (1), and particularly, R ¹ and R ^{2 in} the general formula (1) are hydrogen atoms. The bisphenol F skeleton resin is effective in improving brittleness. In the above general formula (1), when n is less than 3, the primary molecular weight (the molecular weight before curing) is small and the number of functional groups is reduced, so that it is difficult to polymerize, and the dryness to the touch is also reduced. Absent. On the other hand, when n exceeds 9, the primary molecular weight is large. This is not preferable because developability cannot be obtained.

Examples of the polybasic anhydride (a-6) include succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and methyltetrahydro. Drophthalic anhydride, hexane hydrofluoric anhydride, methylhexahydrohydrofluoric anhydride, trialkyltetrahydrofluoric anhydride, methylhymic anhydride, trimeric anhydride, Pyromellitic anhydride, 5- (2,5-dioxotetrahydrofuryl) -1,3-methyl_3-cyclohexene-1,2-dicarboxylic anhydride, benzophenonetetracarboxylic anhydride, chlorendic anhydride, etc. No. These polybasic acid anhydrides can be used alone or in combination of two or more.

If the weight average molecular weight of the resin compound (A) is less than 2,000, the strength of the coating film is reduced, and it is not preferable because it is difficult to obtain the dryness to the touch required for contact exposure. On the other hand, when the weight average molecular weight exceeds 40,000, development with an aqueous alkali solution becomes difficult, which is not preferable. If the acid value of the above resin compound (A) is less than 50 mg KOH / g, development with an aqueous solution of Alkyri becomes difficult, and the thermosetting group becomes insufficient, and the properties of the coating film after thermosetting are reduced Is not desirable because it decreases. On the other hand, when the acid value exceeds 25 Omg KOHZg, it is difficult to obtain development resistance after photocuring, which is not preferable.

As the compound (B) having one or more (meth) acryloyl groups in one molecule and having a carboxyl group and having a weight average molecular weight of 300 to 1,500, A compound obtained by reacting a compound (b—: I) having at least one (meth) acryloyl group and at least one alcoholic hydroxyl group with a polybasic acid anhydride (b-2) Can be suitably used.

Examples of the compound (b-1) having one or more (meth) acryloyl groups and one or more alcoholic hydroxyl groups in one molecule include 2-hydroxyhexyl acrylate and 2-hydroxy. Propyl acrylate, 2-hydroxy methacrylate, 2-hydroxy propyl methacrylate, 4-hydroxy butyl acrylate, 4-hydroxy butyl methacrylate, Pennis Ellis Known and commonly used (meth) acrylate compounds such as Retort Reacrylate, Penri Erythritol Recrylate, Ji Pen Eri Erythri Repent Acrylate, Dipen Eri Erythri Retriene Pentamethacrylate And (meth) acrylic acid esters of monoepoxy compounds such as butylglycidyl ether, phenyldaricidyl ether, glycidyl methacrylate, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and the like. Examples include (meth) acrylic acid esters of hydrogenated epoxy compounds, and among these, compounds having two or more (meth) acryloyl groups are more preferable for increasing sensitivity. These compounds can be used alone or in combination of two or more.

Examples of the polybasic anhydride (b-2) include succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, dodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and methyl terephthalic anhydride. Trahydrophthalic anhydride, hexahydrofluoric anhydride, methylhexahydrofluoric anhydride, trialkyl tetrahydrofluoric anhydride, methylhymic anhydride, trimellitic anhydride , Pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyl-3,4,3 ', 4'-tetracarboxylic dianhydride, diphenyl ether-3,4, 3 ', 4'-Tetracarboxylic dianhydride, 5 — (2,5-Dioxotetrahydrofuryl) — 3 —Methyl-13-cyclohexene-1,2,2-dicarbonic anhydride, 1,2, 3, 4 — butante Examples include tracarboxylic dianhydride, 1,2,3,4-cyclopentenetetracarboxylic dianhydride, and chlorendic anhydride. Of these, anhydrous Pirome Li Uz DOO acid, Benzofuwenonte tetracarboxylic dianhydride, biphenyl - 3, 4, 3 ', 4 ⁷ - Te Torakarubo Nsan'ni anhydride, Jifue two ether - 3,, 3 ^f, 4'-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) 1-3-methyl-13-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-butane Tetrabasic acid anhydrides, such as tetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarbonic dianhydride, are preferred because they can increase the number of photosensitive groups and thermosetting groups. , 5— (2, 5—dioxotetrahydrofur π

) — 3-Methyl-3-cyclohexene-1,2,2-dicarboxylic anhydride, 1,2,3,4-butanetracarboxylic dianhydride, 1,2,3,4-cyclopentenetetra Alicyclic tetrabasic acid anhydrides such as carboxylic dianhydride are more preferred because of their good light transmission and thermosetting properties. These polybasic acid anhydrides can be used alone or in combination of two or more.

The compounding amount of the compound (Β) having two or more (meth) acryloyl groups in one molecule and having a carboxyl group and having a weight average molecular weight of 300 to 1,500 is as follows. The proportion is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, based on 100 parts by mass of the resin compound (Α). If the compounding amount of the above compound (II) is less than 5 parts by mass, the photocurability is lowered, and it is necessary to add another photosensitive compound, which is not preferable. On the other hand, when the amount exceeds 100 parts by mass, it is difficult to obtain the dryness to the touch required for contact exposure and the coating properties such as heat resistance are undesirably reduced.

Examples of the photoradical polymerization initiator (C) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone, 2,2 dimethoxy 1,2-phenylacetophenone, 2,2-diethoxy-1,2-phenylacetophenone, 1,1-dichloroacetophenone, 1- [4- (4-benzoylphenylsulfanyl) 1-2-methyl-1- (4-methylphenyl) Sulfanyl) propane—acetophenones such as 1-one; 2-methyl-1- [4- (methylthio) phenyl] —2-morpholinoaminopropanone 1-1,2-benzyl-12-dimethylamino-1— (4 —Morpholinofenyl) —aminoacetophenones such as butanone-1; 2-methylanthraquinone Anthraquinones, such as 2-ethylanthraquinone, 2-butyl-anthraquinone, and 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-dimethylthioxanthone, 2-clothyloxanthone, Thioxanthones such as 2,4-diisopropylthioxanthone; ketones such as acetophenone dimethyl ketone and benzyl dimethyl ketal; benzophenones such as benzophenone and xanthones; And a compound represented by the general formula (2) (a novel photoradical polymerization initiator manufactured by Chipa Specialty Chemicals, hereinafter abbreviated as CGI-325).

(2)

Among them, CGI-325 represented by the above general formula (2) is hardly soluble in organic solvents, so that a coating film excellent in dryness to the touch can be obtained. It is particularly preferable because it efficiently generates radicals in a small amount with respect to ultraviolet rays having a wavelength of 300 to 400 nm and is used for photopolymerization, and is difficult to sublimate by heat during heat curing or laser exposure.

These photo-radical polymerization initiators for known bonds can be used alone or in combination of two or more, and one or two types of known and commonly used photosensitizers such as tertiary amines can be used. It can be used in combination with the above.

The mixing ratio of the photo-radical polymerization initiator (C) is suitably from 1 to 30 parts by mass, preferably from 2 to 25 parts by mass, based on 100 parts by mass of the photopolymerizable components (A and B). Parts by weight. If the amount of the photo-radical polymerization initiator used is less than the above range, the photocurability deteriorates, while if it is too large, the properties as a solder resist are undesirably deteriorated.

Examples of the epoxy resin (D) include various commonly used epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, brominated bisphenol A type epoxy resin, hydrogenated bis Phenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, brominated phenol novolak type epoxy resin, bisphenol A nopolak type epoxy resin Glycidyl ether such as Compounds: glycidyl ester compounds such as terephthalic acid diglycidyl ester, hexaldehyde diglycidyl phthalate, and dimer acid diglycidyl ester; triglycidyl isocyanurate, N, N, N ', N'-tetraglycidylme Known and commonly used epoxy compounds such as evening xylenediamine, glycidylamine compounds such as N, N, N ', N'-tetraglycidyl bisaminomethylcyclohexane, and N, N-diglycidyladiline. These epoxy resins (D) can be used alone or in combination of two or more.

The mixing ratio of these epoxy resins (D) is 0.6 to 1.8 equivalents to the total amount of the carboxyl groups of the resin compound (A) and the compound (B). It is preferable in terms of properties such as heat resistance, electrical insulation, and adhesion to copper foil of the cured coating film after thermal curing.

The photo-curable and thermo-curable resin composition of the present invention is used for improving properties such as adhesion, hardness, and soldering heat resistance of the cured coating film. Known inorganic fillers can be blended. The mixing ratio of these inorganic fillers is 1 per 100 parts by mass of the resin compound (A).

A ratio of not more than 100 parts by mass is appropriate, and preferably 5 to 100 parts by mass. If the amount is larger than the above range, it is not preferable because the strength of the coating film and the sensitivity are lowered.

Further, the photo-curable and thermo-curable resin composition of the present invention may contain, if necessary, a known and commonly used coloring pigment, coloring dye, thermal polymerization inhibitor, thickener, defoaming agent, leveling agent, cup, and the like. A ring agent and the like can be compounded.

If necessary, an imidazole salt / boron trifluoride complex, an organic metal salt, or the like can be added as a latent curing catalyst. Further, for the purpose of preventing the oxidation of copper in the circuit of the printed wiring board, compounds such as adenine, vinyltriazine, dicyandiamide, orthotrilbiguanide, and melamine, or salts thereof can be added. The compounding ratio of these compounds is suitably not more than 20 parts by mass per 100 parts by mass of the resin compound (A). By adding these, the chemical resistance of the cured coating film and the copper The adhesion to the foil is improved. Further, the photocurable and thermosetting resin composition of the present invention is required in order to adjust the composition to a viscosity suitable for a coating method and to further increase the sensitivity as long as the effects of the present invention are not impaired. A diluent can be added according to the requirements. As the diluent, an organic solvent and / or a reactive diluent can be used.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol ethers such as glycol methyl ether, triethylene glycol monoethyl ether, etc .; ethyl acetate, butyl acetate, ethylene glycol Noethyl ether acetate, ethylene glycol monobutyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Acetates such as propylene glycol monobutyl acetate and dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or as a mixture of two or more. The amount of the organic solvent can be set to an arbitrary amount according to the coating method.

Representative examples of the reactive diluent include hydroxyalkyl acrylates such as 2-hydroxyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol Mono- or diacrylates of glycols such as diethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide and other acrylamides; N, -dimethylaminoethylacrylate, N, N-dimethyla Aminoalkyl acrylates such as minopropyl acrylate; phenols such as hexanediol, trimethylolpropane, pentaerythritol, dipentyl erythritol, and tris-hydroxyl-isocyanurate; Polyhydric alcohols such as polyhydric alcohols or their ethylene oxide adducts or propylene oxide adducts; phenoxyacrylates, bisphenol A diacrylates, and ethylene oxide adducts or propylene oxide of these phenols; Acrylates such as adducts; Glycidyl ether acrylates such as phosphoglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and melamine acrylate, and Z or the above acrylate Each methacrylate and the like can be mentioned.

The photocurable and thermosetting resin composition of the present invention is applied to a printed wiring board on which a circuit is formed by a method such as a screen printing method, a force coating method, a spray coating method, or a roll coating method. By evaporating (temporarily drying) the organic solvent contained in the composition at a temperature of about 100 ° C., a coating film having excellent dryness to the touch and a long development life can be formed. After that, it is selectively exposed to actinic light through a patterned photomask, or laser-direct imaging method, in which an image is directly printed on a printed wiring board by CAD data from a computer. The exposed part can be developed, and the unexposed part can be developed with a dilute aqueous solution to form a resist pattern.Then, for example, it can be heated to a temperature of about 140 to 180 ° C and thermally cured. As a result, an insulating coating film having excellent adhesion, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulation, and corrosion resistance is formed.

As the dilute aqueous alkali solution, a dilute aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used. Further, as an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp or a metal halide lamp, and a carbonic acid laser are used. Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. However, it goes without saying that the present invention is not limited to the following Examples. In the following, “part j” and “%” are based on mass unless otherwise specified.

Synthesis example 1

In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, cresol novolak epoxy resin (Epiclone N-680, manufactured by Dainippon Ink and Chemicals, epoxy equivalent = 210) 2 10 9 and 4 parts of carbitol acetate were weighed out and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise, and reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C, 76.1 parts of tetrahydrophthalic anhydride was added, and the infrared absorption analysis was repeated until the acid anhydride absorption peak (1780 cm- ¹ ) disappeared. The reaction was performed for about 8 hours. To this reaction solution, 6.4 parts of aromatic solvent Ivuzol # 150096 manufactured by Idemitsu Petrochemical Co., Ltd. was added, diluted and taken out.

The thus obtained reaction solution containing the resin compound (A) having two or more acryloyl groups and a carboxyl group had a nonvolatile content of 65% and a solid acid value of 78 mgKOH / g. Hereinafter, this reaction solution is referred to as A-1 varnish. Synthesis example 2

In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, 10 parts of cresol novolak-type epoxy resin Epiclone N-680210 and 129.5 parts of carbitol acetate were weighed and dissolved by heating. Next, 0.1 part of hydroquinone was used as a polymerization inhibitor, and triphenylphosphine was used as a reaction catalyst. 2.0 parts were added. The mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for about 16 hours until the acid value became 3.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C, 106.5 parts of tetrahydrofuran anhydride was added, and the absorption peak of the acid anhydride was determined by infrared absorption analysis. The reaction was continued for about 8 hours until 1780 cm- ¹ ) disappeared. To this reaction solution was added 3.44 parts of an aromatic solvent, ibusol # 1500143.4, for dilution. Furthermore, a varnish obtained by dissolving 75 parts of bisphenol A type epoxy resin (Epicoat 101, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent = 475) in 25 parts of carbitol acetate 5 5. 4 parts were gradually added dropwise and reacted for about 12 hours until the acid value became stable.

The thus obtained reaction solution containing the resin compound (A) having two or more acryloyl groups and a carboxyl group had a nonvolatile content of 60% and an acid value of a solid of 79 mg KOH / g. Hereinafter, this reaction solution is referred to as A-2 varnish. Synthesis example 3

In a flask equipped with a thermometer, an agitator, a dropping funnel, and a reflux condenser, a hydrogenated product of bisphenol A type epoxy resin (epikoto YX800, manufactured by Japan Epoxy Resin Co., Ltd.) Equivalent = 202) 22.0 parts and 97.8 parts of carbitol acetate were weighed out and heated to about 90 ° C. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 ° C., and 7.2.7 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for about 24 hours until the acid value became 2.O mgKO HZg or less. To this reaction solution was added an alicyclic tetrabasic acid anhydride, 51- (2,5-dioxotetrahydrofurfuryl) —3-methyl-3-cyclohexene-1,2, -dicarboxylic anhydride (Dainippon Ink. 88.0 parts of Ebicron B4400) (manufactured by Chemical Industry Co., Ltd.) was added, and the mixture was reacted by infrared absorption analysis for about 8 hours until the absorption beak (1780 cm- ¹ ) of the acid anhydride disappeared. . To this reaction solution was added and diluted an aromatic solvent ivuzol # 1507.98 parts.

The reaction solution containing the resin compound (A) having two or more acryloyl groups and a carboxyl group obtained in this manner has a nonvolatile content of 65% and an acid value of solid substance. It was 102 mgKOH / g. Hereinafter, this reaction solution is referred to as A-3 varnish. Synthesis Example 4

In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, a bisphenol F-type epoxy resin having an epoxy equivalent of 800 [the average value of n in the general formula (1) is 5. It is 0. After dissolving 400 parts in 92.5 parts of epichlorohydrin and 460 parts of dimethyl sulfoxide, 91.2% Na0H81.2 parts in 100 parts was stirred at 70 ° C. under stirring at 100 ° C. Added over minutes. After the addition, the mixture was further reacted at 70 ° C. for 3 hours, and then excess epichlorohydrin and dimethyl sulfoxide were distilled off under reduced pressure. After adding and dissolving 75 parts of methylisobutyl ketone to the obtained reaction product, 10 parts of a 30% Na0H aqueous solution was further added, and the mixture was reacted at 70 ° C. for 1 hour. 200 g of ion-exchanged water was added to this solution, and the mixture was washed with water. After repeating this water washing operation twice, the oil layer was taken out, methyl isobutyl ketone was distilled off under reduced pressure, and an epoxy resin having an epoxy equivalent of 290 was taken out.

The epoxy resin (290 parts) was weighed and placed in a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux cooler, and carbitol acetate (31.2 parts) was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. The mixture was heated to 95 to 105 ° C, and 72.7 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for about 24 hours until the acid value became 2.0 mgKOH / g or less. The reaction product was cooled to 80 to 90 ° C., and 106.5 parts of tetrahydrofuroic anhydride was added, and the absorption peak of acid anhydride (178 The reaction was carried out for about 10 hours until 0 cm- ¹ ) disappeared.

The reaction solution thus obtained containing the resin compound (A) having two or more acryloyl groups and a carboxyl group has a nonvolatile content of 60% and an acid value of solid of 71.8 mg K 0 H / g. Hereinafter, this reaction solution is referred to as A-4 varnish.

Synthesis example 5 In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 200 parts of pen erythritol triacrylate (PE-3A, manufactured by Kyoeisha Yushi Co., Ltd.) and 0.1 part of hydroquinone as a polymerization inhibitor And 1.0 part of triphenylphosphine as a reaction catalyst, followed by 40 parts of 5- (2,5-dioxotetrahydrofuryl) -1,3-methyl-3-cyclohexene-1,2,2-dicarboxylic anhydride and carbitol 26.7 parts of acetate were added, and the mixture was reacted for about 8 hours until the absorption peak of acid anhydride (1780 cm- ¹ ) disappeared by infrared absorption analysis.

The reaction solution containing the compound (B) having one or more (meth) acryloyl groups in one molecule and having a carboxyl group in one molecule thus obtained has a non-volatile content of 90% and a solid content of 90%. The acid value was 7 lmg KOHZ. Hereinafter, this reaction solution is referred to as B-1 varnish.

Synthesis Example 6

Cresol novolak type epoxy resin according to a conventional method (epoxy equivalent = 210, containing on average 4.5 phenolic core residues in one molecule) 1.05 equivalents are reacted with 1 equivalent of acrylic acid, Further, the reaction product obtained by reacting 0.89 equivalents of isophorone diisocyanate with 0.79 equivalents of phenol erythritol triacrylate was diluted with carbitol acetate to a non-volatile content of 70%. This was a solution of an active energy ray-curable resin having an average of 9.9 acryloyl groups per molecule. Hereinafter, this resin solution is referred to as epoxy urethane acrylate C.

Example 1

Using the A-1 varnish and B-1 varnish obtained in Synthesis Example 1 and Synthesis Example 5, the following components were kneaded with a three-roll mill to obtain a photo-curable and thermo-curable resin composition. Main agent 1 was obtained.

Main agent 1

A-1 Varnish 90 parts

B-1 Varnish 28 parts Irgacure 907 12 parts (Photo-radical polymerization initiator manufactured by Ciba Specialty Chemicals) Phthalocyanine Green 0.5 part Dicyandiamide 0.3 part Silicone-based defoamer 1 part Barium sulfate 20 parts Siliency 20 parts Fine powder silica (thickening 6 parts Dipropylene glycol monomethyl ether 8 parts Total 18.5.8 parts As the curing agent composition of the main agent 1, the following compounding components using the epoxy urethane acrylate C obtained in Synthesis Example 6 were used. The roll was milled to obtain a curing agent 1 for the photocurable and thermosetting resin composition.

Curing agent 1

Pen Eri Erythritol Tol acrylate .36 parts Melamine 10 parts Epoxy urethane acrylate C 20 parts Pheno-novolak epoxy resin 27 parts

(Dow Chemical Co., DEN—4 3 8)

Bixylenol diglycidyl ether 36 parts Barium sulfate 27 parts Carbitol acetate 40 parts Total 19 6 parts Main ingredient 1 composition 70 parts by weight and curing agent 1 composition 30 parts by weight By mixing, a photocurable and thermosetting resin composition was obtained.

Example 2

Similarly, the following components using the A-2 varnish and the B-1 varnish obtained in Synthesis Examples 2 and 5 were kneaded with a three-roll mill to obtain a photocurable and thermosetting resin composition. The main agent 2 was obtained.

Main agent 2 A-2 Varnish 9 0 parts

B-1 Varnish 2 8 parts Irgacure 1 9 0 7 1 2 parts Phthalocyanine green 0.5 parts Dicyandiamide 0.3 parts Silicone defoamer 1 part Barium sulfate 20 parts Shiri power 20 parts Fine powder power 6 parts Di Propylene glycol monomethyl ether 18 parts Total 185.8 parts The curing agent 1 prepared in Example 1 was used as the curing agent composition of the main agent 2.

70 parts by mass of the above-mentioned main agent 2 composition and 30 parts by mass of the above-mentioned curing agent 1 composition were mixed to obtain a photocurable and thermosetting resin composition.

Example 3

Similarly, the following components using the A-2 varnish, A-3 varnish and B-1 varnish obtained in Synthesis Example 2, Synthesis Example 3 and Synthesis Example 5 were ground by a three-roll mill, Photocuring The main agent 3 of the thermosetting resin composition was obtained.

Main agent 3

A-2 Varnish 4 0 parts

A-3 Varnish 5 0 parts

B-1 Varnish 2 8 parts Irgacure 1 90 7 1 2 parts Phthalocyanine green 0.5 parts Dicyandiamide 0.3 parts Silicone defoamer 1 part Barium sulfate 20 parts Silica 20 parts Fine silica powder (Thickener) 6 parts Dipropylene glycol monomethyl ether 8 parts Total 15.8.8 parts As the curing agent composition of the main agent 3, the curing agent 1 prepared in Example 1 was used.

70 parts by mass of the above-mentioned main agent 3 composition and 30 parts by mass of the above-mentioned curing agent 1 composition were mixed to obtain a photocurable and thermosetting resin composition.

Example 4

Similarly, the following components using the A-1 varnish and B-1 varnish obtained in Synthesis Example 1 and Synthesis Example 5 were connected in a three-roll mill to form a photocurable and thermosetting resin composition. The main agent 4 was obtained.

Main agent 4

A-1 Varnish 1 0 0 parts

B-1 Varnish 2 5 parts Phthalocyanine green 0.6 parts Dicyandiamide 0.3 parts Silicone defoamer 2 parts Barium sulfate 20 parts Silica 20 parts Fine powder silica (thickening agent) 6 parts Dipropylene glycol monomethyl ester Ter 8_ Total 181.9 parts '' The following components using the epoxy urethane acrylate C obtained in Synthesis Example 6 as a curing agent composition for the main agent 4 were kneaded with a three-roll mill, Curability A curing agent 2 for the thermosetting resin composition was obtained.

Curing agent 2

Epoxy urethane acrylate C 20 parts Melamine 8 parts Phenol novolak type epoxy resin varnish 3 6 parts (Nippon Kayaku Co., Ltd., EPPN—201 carbitol

(Acetate-cured product, nonvolatile content 75 wt%)

Bixylenol diglycidyl ether 36 parts Barium sulfate 20 parts CGI-3 2 5 7 parts

(Ciba 'Specialty' Chemicals

Photo-radical polymerization initiator)

Fine powder powder 2 parts Carbitol acetate 2 5 parts Total 1 5 4 parts 70 parts by weight of the above main agent 4 composition and 30 parts by weight of curing agent 2 composition are mixed to obtain a photo-curing and heat curing A resin composition was obtained.

Example 5

Similarly, the following components using the A-1 varnish, A-4 varnish, and B-1 varnish obtained in Synthesis Example 1, Synthesis Example 4, and Synthesis Example 5 were successively meatned with a three-roll mill, Photocurable The main agent 5 of the thermosetting resin composition was obtained.

Main agent 5

A-1 Varnish 7 0 parts

A-4 Varnish 30 parts B-1 Varnish 2 5 parts Phthalocyanine Green 0.6 parts Dicyandiamide 0.3 parts Silicone defoamer 2 parts Barium sulfate 20 parts Silica 20 parts Fine powder siliency (thickener) 6 parts Dipropylene glycol monomethyl ether 8Ji Total 181.9 parts As the curing agent composition of the main agent 5, the curing agent 2 prepared in Example 4 was used. Was.

70 parts by mass of the above-mentioned main agent 5 composition and 30 parts by mass of the above-mentioned curing agent 2 composition were mixed to obtain a photocurable and thermosetting resin composition.

Comparative Example 1

The following components using the A-1 varnish obtained in Synthesis Example 1 were kneaded with a three-roll mill to obtain a main component 6 of a photocurable and thermosetting resin composition.

Main agent 6

A-1 Varnish 1 2 0 parts Irgacure 1 9 7 1 2 parts Phthalocyanine green 0.5 parts Dicyandiamide 0.3 parts Silicone defoamer 1 part Barium sulfate 20 parts Silica 20 parts Fine powder silica (thickener 6 parts) Dipropylene glycol monomethyl ether 8_¾ Total 187.8 parts The curing agent 1 prepared in Example 1 was used as the curing agent composition of the main agent 6.

70 parts by mass of the above-mentioned main agent 6 composition and 30 parts by mass of the above-mentioned curing agent 1 composition were mixed to obtain a photocurable and thermosetting resin composition.

Comparative Example 2

The following components using the urethane acrylate C synthesized in Synthesis Example 6 were kneaded with a three-roll mill to obtain a curing agent 3 for a photocurable and thermosetting resin composition.

Hardener 3

Pen Yuri Erythritol triacrylate 4 8 parts Melamine 10 parts Epoxy urethane acrylate C 20 parts 27 parts of phenol novolak type epoxy resin (DEN-438) 36 parts of bixylenol diglycidyl ether 36 parts of barium sulfate 30 parts 30 parts of carbitol acetate Total 19 6 parts 6 main ingredients used in Comparative Example 1 above 70 parts by mass of the composition and 30 parts by mass of the above-mentioned curing agent 3 composition were mixed to obtain a photocurable and thermosetting resin composition.

Performance evaluation:

(1) Touch dryness after temporary drying

Each of the photo-curable and thermo-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were coated on a copper-clad substrate by screen printing, respectively, using a hot-air circulation drying furnace. And a substrate dried at 80 ° C. for 30 minutes was prepared, and the dryness to the touch of the coating film surface was evaluated according to the following criteria.

〇: completely non-sticky

Δ: Slightly sticky

X: with a dash

(2) Sensitivity

Each of the photo-curable and thermo-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was entirely applied by screen printing to a printed wiring board on which a circuit was formed. It was dried in an oven at 80 C for 30 minutes. These substrates, against Kodak N o. 2 steps evening breccias DOO, 3 0 mJ / cm ² with and exposure light, 1 minute development in l wt% N a ₂ CO ₃ aqueous spray pressure 2 kg / cm ² Then, the number of stages from which the coating film was completely removed was evaluated.

Each of the photo-curable and thermo-curable resin compositions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was entirely applied by screen printing to a printed wiring board on which a circuit was formed. It was dried in an oven at 80 ° C. for 30 minutes. Applying a negative film solder resist pattern was drawn on these substrates, an exposure amount 3 0 mj / cm ² of exposed in the exposure condition, l wt% of spray pressure 2 kg / cm ² with N a ₂ C 0 ₃ solution Development was performed for 1 minute to form a solder resist pattern. this The substrate was thermally cured at 150 ° C. for 60 minutes to prepare an evaluation substrate, which was subjected to the following performance evaluation of (3) solder heat resistance and (4) electroless plating resistance.

(3) Solder heat resistance

A rosin-based flux is applied to the above-mentioned evaluation board, immersed in a solder bath set at 260 ° C in advance for 30 seconds, and the flux is washed with isopropyl alcohol. The discoloration was evaluated.

〇: No change is observed

△: A slight change such as discoloration

X: The film has swelling or peeling

(4) Electroless gold plating resistance

The above evaluation substrate was subjected to electroless plating using a commercially available electroless nickel plating solution and an electroless plating solution.

The evaluation substrate after the adhesion was subjected to a peel test using an adhesive tape, and the peeling of the resist layer was evaluated.

〇: No change is observed

△: slight change in peeling

: The whole coating has peeling

(5) Electrical insulation

A substrate was prepared under the above conditions using a comb-type electrode B coupon with an IPCB—25 test pattern, a bias of 500 V DC was applied to the comb-type electrode, and the insulation resistance was measured.

Table 1 summarizes these results.

table 1

As is clear from the results shown in Table 1, in Examples 1 to 5 according to the present invention, the dryness of the dry coating film to the touch, the sensitivity, and the solder heat resistance of the cured coating film, the electroless gold plating resistance, It retains satisfactory properties in electrical insulation (however, in Example 1, it has two or more (meth) acryloyl groups in one molecule compared to other Examples, and carboxyl group The resin compound having a group (Α) has a low molecular weight, and the dryness to the touch is slightly inferior to the other examples due to the effect of the solubility of the photo-radical polymerization initiator.) Only the resin compound (Α) In Comparative Example 1 in which the compound (Β) was not added to the compound, the sensitivity was poor. On the other hand, Penno Erythritol Triacrylate, a low molecular weight compound having two or more (meth) acryloyl groups in one molecule, was used. In Comparative Example 2 where a large amount was blended, Poor touch drying properties, also was inferior in an electroless gold-plating resistance. Further, in Examples 4 and 5 using the photo-radical polymerization initiator represented by the general formula (2), the sensitivity was low even though the amount of the photo-radical polymerization initiator was reduced to about 1Z3. Rose. Industrial applicability

As described above, the photocurable and thermosetting resin composition of the present invention has high sensitivity, stable resolution even when the film thickness of the coating film changes, It retains excellent properties such as dryness, heat resistance of cured coating, electrical insulation, etc., and does not peel cured coating during electroless plating. It is suitable for the formation of solder resist for printed wiring boards and the formation of intermediate insulating layers of printed wiring boards by the build-up method. By using the photo-curable and thermo-curable resin composition of the present invention for forming an interlayer insulating layer and / or a solder resist layer of a printed wiring board, the exposure time can be reduced. In addition, if laser direct imaging is used, a film such as a negative film is not required.

Claims

The scope of the claims

1. (A) A molecule having two or more (meth) acryloyl groups in one molecule, having a carboxyl group, having a weight average molecular weight of 2,000 to 40,000, and an acid value of 50 to 250 mgKOH / g. A resin compound, (B) a compound having at least one (meth) acryloyl group in one molecule and having a carboxyl group and a weight average molecular weight of 300 to 1,500, (C) a photoradical polymerization initiator, And (D) a photocurable / thermosetting resin composition containing an epoxy resin.

2. The resin (a) having two or more (meth) acryloyl groups and two or more carboxyl groups in one molecule is a resin (a-1) having two epoxy groups in one molecule. 2. The composition according to claim 1, which is a resin obtained by reacting a bifunctional epoxy resin (a-2) having a group.

3. After the resin compound (A) is reacted with a (meth) acrylic acid (a-3) on a bifunctional epoxy resin (a-2) having two epoxy groups in one molecule, The composition according to claim 1, which is a resin obtained by reacting an acid anhydride (a-4).

4. The bifunctional epoxy resin (a-2) having two epoxy groups in one molecule is a hydrogenated product of bisphenol A diglycidyl ether or bisphenol F diglycidyl ether. Item 4. The composition according to Item 2 or 3.

5. The composition according to claim 3, wherein the tetrabasic anhydride (a-4) is an aliphatic tetrabasic anhydride.

6. After the above resin compound (A) is reacted with (meth) acrylic acid (a-3) on a polyfunctional epoxy resin (a-5) represented by the following general formula (1), 2. The composition according to claim 1, which is a resin obtained by reacting an anhydride (a-6).

(In the formula, R ¹ and R ² represent a hydrogen atom or a methyl group, R ³ represents a hydrogen atom or a glycidyl group, and n is a number from 3 to 9.)

7. The compound (B) has one or more (meth) acryloyl groups and one or more alcoholic hydroxyl groups in one molecule, and the compound (b-1) has a polybasic acid anhydride (b-2) 3. The composition according to claim 1, which is a compound obtained by reacting the composition.

8. The composition according to claim 1, wherein the amount of the compound (B) is 5 to 100 parts by mass based on 100 parts by mass of the resin compound (A).

9. The composition according to claim 1, wherein the photo-radical polymerization initiator is a compound represented by the following general formula (2).

10. A printed wiring board comprising an interlayer insulating layer and a Z or solder-resist layer formed from the photocurable and thermosetting resin composition according to claim 1.

Summary The photocurable and thermosetting resin composition has (A) two or more (meth) acryloyl groups in one molecule and a carboxyl group having a weight average molecular weight of 2,000 to 40. 000, a resin compound having an acid value of 50 to 250 mg K 0 H / g, and (B) a compound having two or more (meth) acryloyl groups in one molecule and having a carboxyl group having a weight average molecular weight of 300 to 1,500 compounds, (C) a radical photopolymerization initiator, and (D) an epoxy resin. Such a photocurable and thermosetting resin composition is suitable for forming a solder resist for manufacturing a printed wiring board, forming an intermediate insulating layer of a printed wiring board by a build-up method, and the like.