WO2017056663A1 - Curable composition for inkjet, cured coating film using same and printed wiring board - Google Patents

Abstract

Provided are: a curable composition for inkjet, which exhibits good adhesion to a base in addition to having various characteristics such as solder heat resistance and resistance to gold plating, and which has low viscosity suitable for inkjet printing in addition to high hardness after curing; a cured coating film which is obtained by curing this curable composition for inkjet; and a printed wiring board which has this cured coating film on a substrate. A curable composition for inkjet, which contains (A) a urethane (meth)acrylate resin having a functionality of 5-12 (inclusive) and (B) a photopolymerization initiator.

Description

Curable composition for inkjet, cured coating film and printed wiring board using the same

The present invention relates to an inkjet curable composition (hereinafter also simply referred to as “curable composition”) used for inkjet printing, a cured coating film using the same, and a printed wiring board.

In recent years, as a method for forming a coating film of an etching resist, a solder resist, a symbol marking or the like on a printed wiring board, an ink jet printing method has attracted attention (Patent Document 1).

International Publication No. 2004/099272

On the other hand, various curable compositions for printed wiring boards such as resist inks and marking inks formed on printed wiring boards have good adhesion to conductive layers such as conductive circuit metals and substrates such as plastic substrates. It is required to have solder heat resistance and gold plating resistance under more severe conditions while having high hardness after curing.

However, in a composition used for inkjet printing, it has been difficult in terms of design to satisfy the printability (applicability) of the inkjet method and satisfy all the required performance as described above.

Accordingly, an object of the present invention is to provide an ink jet having good adhesion to the base in addition to various properties such as solder heat resistance and gold plating resistance, high hardness after curing, and low viscosity suitable for ink jet printing. It is to provide a curable composition for use, a cured coating film using the same, and a printed wiring board.

As a result of intensive studies, the present inventors have found that the above problem can be solved by a curable composition containing a urethane (meth) acrylate resin having a predetermined functional number and a photopolymerization initiator, and to complete the present invention. It came.

That is, the curable composition for inkjet of the present invention is
(A) a urethane (meth) acrylate resin having 5 to 12 functional groups;
(B) a photopolymerization initiator;
It is characterized by including.

In the curable composition of the present invention, the (A) urethane (meth) acrylate resin preferably has a viscosity at 25 ° C. of 1,000 to 20,000 mPa · s. Further, the curable composition of the present invention further includes (C) a thermosetting compound having at least one thermoreactive functional group (excluding an epoxy (meth) acrylate resin having at least one (meth) acryloyl group). The (C) thermosetting compound (excluding an epoxy (meth) acrylate resin having at least one (meth) acryloyl group) as the at least one (meth) acryloyl group and at least one thermal reaction It is preferable that the 1st thermosetting compound which has a functional functional group, and the 2nd thermosetting compound which has an at least 2 thermoreactive functional group are included. Furthermore, the curable composition of the present invention preferably further comprises (D) an epoxy (meth) acrylate resin having at least one (meth) acryloyl group, and the (D) epoxy (meth) acrylate resin is A bisphenol-type epoxy (meth) acrylate resin is preferred. Furthermore, the curable composition of the present invention preferably further comprises (E) a bifunctional (meth) acrylate compound, and the (E) bifunctional (meth) acrylate compound has 4 to 12 carbon atoms. A compound having an alkylene chain is preferred. Furthermore, the curable composition of the present invention preferably has a viscosity at 50 ° C. of 50 mPa · s or less.

The cured coating film of the present invention is characterized by curing the curable composition for inkjet of the present invention.

The printed wiring board of the present invention has the above-described cured coating film of the present invention on a substrate.

According to the present invention, in addition to various properties such as solder heat resistance and gold plating resistance, it has good adhesion to the base, has high hardness after curing, and has a low viscosity suitable for inkjet printing. It became possible to implement | achieve the curable composition, the cured coating film using this, and a printed wiring board.

Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, the curable composition means a composition that is cured by light, heat, or both. The term “(meth) acrylate” is a general term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.

The curable composition for inkjet of the present invention is characterized by comprising (A) a urethane (meth) acrylate resin having 5 to 12 functional groups and (B) a photopolymerization initiator.

[(A) Urethane (meth) acrylate resin having 5 to 12 functional groups]
(A) Urethane (meth) acrylate resin is a compound having a plurality of urethane bonds and a plurality of (meth) acryloyl groups. Examples of pentafunctional urethane (meth) acrylate resins that can be used in the present invention include DM850 manufactured by DOUBLE BOND CHEMICAL, and Hitaloid 7903-1 manufactured by Hitachi Chemical. In addition, as the hexafunctional urethane (meth) acrylate resin, U-6LPA and UA-1100H manufactured by Shin-Nakamura Chemical Co., Ltd., CN975 manufactured by Sartomer Co., Ekacryl 220 manufactured by Daicel Ornex Co., KRM8200AE, Ekacryl 8254, Ekacryl 8301R, DM527, DM528, DM571, DM576, DM776, DM87A, DM88A manufactured by DOUBLE BOND CHEMICAL, Hitachi 9790-1, TA24-195H manufactured by Hitachi Chemical, and the like.

Furthermore, examples of the 9-functional urethane (meth) acrylate resin include KRM 8904 manufactured by Daicel-Ornex, Hitaroid 7903-3, and Hitaloid 7903-B manufactured by Hitachi Chemical. Furthermore, examples of the 10-functional urethane (meth) acrylate resin include KRM8452 manufactured by Daicel Ornex, DM588 manufactured by DOUBLE BOND CHEMICAL, and the like. Furthermore, examples of the 12-functional urethane (meth) acrylate resin include DOUBLE BOND, CHEMICAL DM5812, and Hitachi Chemical's Hitaroid 7903-4. These urethane (meth) acrylate resins can be used alone or as a mixture of two or more.

(A) The urethane (meth) acrylate resin has a viscosity of 1,000 to 20,000 mPa · s, particularly 1,000 to 10,000 mPa · s at 25 ° C. in order to keep the viscosity of the entire composition low. Is preferred. By using a relatively low viscosity (A) urethane (meth) acrylate resin and keeping the viscosity of the entire composition low, the injection property and stability during ink jet printing become good. By using a urethane (meth) acrylate resin having 5 or more functional groups, heat resistance is improved, and by using a urethane (meth) acrylate resin having 12 or less functional groups, flexibility can be imparted to the formed coating film. Properties such as adhesion can be improved. More preferably, it is 8 functionals or less, More preferably, it is 6 functionals or less.

(A) The blending amount of the urethane (meth) acrylate resin is preferably 0.5 to 60 parts by mass, more preferably 1.5 to 55 parts by mass in 100 parts by mass of the curable composition. By setting the blending amount of the urethane (meth) acrylate resin to 0.5 parts by mass or more, good solder heat resistance and gold plating resistance can be ensured. Moreover, the viscosity of a curable composition can be restrained low by making the compounding quantity of urethane (meth) acrylate resin 60 mass parts or less, and the injection property and stability at the time of inkjet printing can be ensured favorably.

[(B) Photopolymerization initiator]
(B) It does not specifically limit as a photoinitiator, For example, a photoradical polymerization initiator can be used. As the radical photopolymerization initiator, any compound can be used as long as it is a compound that generates radicals by light, laser, electron beam or the like and initiates radical polymerization reaction.

Examples of the radical photopolymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; 2-hydroxy-2-methyl-1-phenyl-propan-1-one Acetophenones such as alkylphenone, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- ( Aminoacetophenones such as methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone ; 2-methyl Anthraquinones such as anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthones; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutyrate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole Thiol compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone and other organic halogen compounds; Benzophenones or xanthones such as 4,4'-bisdiethylaminobenzophenone; acylphosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Examples include fin oxides.

These known and commonly used photopolymerization initiators can be used alone or as a mixture of two or more thereof. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4- Photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine, triethanolamine can be added.

Also, titanocene compounds such as Irgacure 784 (manufactured by BASF Japan) having absorption in the visible light region can be added to promote the photoreaction. The photopolymerization initiator and the photoinitiator aid are not particularly limited to these, as long as they absorb light in the ultraviolet or visible light region and radically polymerize unsaturated groups such as (meth) acryloyl groups. Not limited, it can be used alone or in combination.

Examples of commercially available products include Irgacure 261, 184, 369, 651, 500, 819, 907, 784, 2959, Irgacure 1116, 1173, Irgacure TPO (trade name, manufactured by BASF Japan), Ezacure KIP150, KIP65LT. , KIP100F, KT37, KT55, KTO46, KIP75 / B, ONE (trade name, manufactured by Fratelli Lamberti), and the like.

(B) The blending ratio of the photopolymerization initiator is preferably in the range of 1 to 25 parts by weight, more preferably in the range of 5 to 20 parts by weight, in 100 parts by weight of the curable composition of the present invention. Is particularly preferred. (B) By setting the blending ratio of the photopolymerization initiator in the above range, appropriate photocurability can be obtained.

[(C) Thermosetting compound having at least one thermoreactive functional group (excluding epoxy (meth) acrylate resin having at least one (meth) acryloyl group)]
(C) The thermoreactive functional group of the thermosetting compound includes a hydroxyl group, a carboxyl group, an isocyanate group, an amino group, an imino group, an epoxy group, an oxetanyl group, a mercapto group, a methoxymethyl group, a methoxyethyl group, and an ethoxymethyl group. A known and commonly used thermosetting functional group such as at least one selected from the group consisting of ethoxyethyl group and oxazoline group, cyclic (thio) ether group, (cyclo) carbonate group, episulfide group, and polyoxazoline group More preferably, from the group consisting of hydroxyl group, carboxyl group, isocyanate group, amino group, imino group, epoxy group, oxetanyl group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group and oxazoline group At least one functional group selected.

(C) The heat-reactive compound preferably has at least one (meth) acryloyl group in addition to at least one heat-reactive functional group. In general, a compound having a monofunctional heat-reactive functional group has a low molecular weight, which causes a problem that it volatilizes at the same time as the reaction by heat proceeds at the time of thermosetting, but by having a (meth) acryloyl group It becomes possible to polymerize at the time of temporary curing by light in ink jet printing and to obtain good characteristics without volatilization at the time of main curing by heat.

In the present invention, in particular, the (C) thermosetting compound includes a first thermosetting compound having at least one (meth) acryloyl group and at least one thermoreactive functional group, and at least two thermoreactive compounds. It is preferable to use together with the 2nd thermosetting compound which has a functional group. Thereby, it becomes possible to improve solder heat resistance more.

Among the above-mentioned heat-reactive functional groups, specific examples of hydroxyl groups include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meta ) Acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc., and commercially available products include light ester HO, light ester HOP, light ester HOA (above, Kyoeisha Chemical Co., Ltd.) Product name).

Specific examples of the thermosetting compound in which the thermoreactive functional group is a carboxyl group include acrylic acid, methacrylic acid, acrylic acid dimer, 2-methacryloyloxyethyl succinic acid, methacryloyloxyethyl hexahydrophthalic acid, Examples include phthalic acid monohydroxyethyl acrylate, and commercially available products include LIGHT ESTER HO-MS, LIGHT ESTER HO-HH (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-5400 (Toagosei Co., Ltd. ) Product name).

Specific examples of the thermosetting compound in which the heat-reactive functional group is an isocyanate group include 2-methacryloyloxyethyl isocyanate (for example, trade name, MOI manufactured by Showa Denko KK).

Specific examples of the thermosetting compound in which the thermoreactive functional group is an amino group include acrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, Examples thereof include N, N-diethylaminoethyl methacrylate.

Specific examples of the thermosetting compound in which the thermoreactive functional group is an epoxy group include glycidyl methacrylate, (meth) acryloyl group-containing alicyclic epoxy resin, (meth) acryloyl group-containing bisphenol A type epoxy resin, and the like. Can be mentioned. Examples of commercially available (meth) acryloyl group-containing alicyclic epoxy resins include Cyclomer M100, Cyclomer A200, Cyclomer 2000 (above, trade name manufactured by Daicel Corporation), and the like. Examples of commercially available (meth) acryloyl group-containing bisphenol A type epoxy resins include NK Oligo EA-1010N, EA-1010LC, EA-1010NT (above, trade names manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

Specific examples of the thermosetting compound whose heat-reactive functional group is an oxetanyl group include oxetane (meth) acrylate and the like, and commercially available products include OXE-10 and OXE-30 (Osaka Organic Chemical Co., Ltd.). Product name).

Specific examples of thermosetting compounds in which the thermoreactive functional group is a mercapto group include ethylthioacrylate, ethylthiomethacrylate, biphenylthioacrylate, biphenylthiomethacrylate, nitrophenylthioacrylate, nitrophenylthiomethacrylate, and triphenyl. 2 of methylthioacrylate, triphenylmethylthiomethacrylate, 1,2-bis [(2-mercaptoethyl) thio] -3-mercaptopropane trisacrylate, 2-propenoic acid 2- (mercaptomethyl) -methyl ester, methacrylic acid 2 -[(2-mercaptoethyl) thio] ethyl ester and the like.

Specific examples of the thermosetting compound in which the thermoreactive functional group is a methoxymethyl group include methoxymethyl acrylate, methoxymethyl methacrylate, dimethoxymethyl acrylate, dimethoxymethyl methacrylate, and the like, and commercially available products include Nicarak MX. -302 (acrylic-modified alkylated melamine, trade name manufactured by Sanwa Chemical Co., Ltd.).

Specific examples of the thermosetting compound in which the thermoreactive functional group is a methoxyethyl group include 1-methoxyethyl acrylate, 1-methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate, 1,1 -Methoxyethyl acrylate, 1,1-methoxyethyl methacrylate and the like.

Specific examples of the thermosetting compound in which the thermoreactive functional group is an ethoxyethyl group include 1-ethoxyethyl acrylate, 1-ethoxyethyl methacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethyl methacrylate and the like. .

Specific examples of the thermosetting compound in which the thermoreactive functional group is an ethoxymethyl group include N-ethoxymethylacrylamide, N-ethoxymethylmethacrylamide, ethoxymethyl acrylate, ethoxymethyl methacrylate and the like.

Specific examples of thermosetting compounds in which the thermoreactive functional group is an oxazoline group include 2-methyl-2-{[3- (4,5-dihydro-2-oxazoyl) benzoyl] of 2-propenoic acid] Amino} ethyl ester, 2-methyl-2- (4,5-dihydro-2-oxazoyl) ethyl ester of 2-propenoic acid, 3- (4,5-dihydro-4,4-dimethyl- of 2-propenoic acid 2-oxazoyl) propyl ester and the like.

Examples of thermosetting compounds having two or more thermoreactive functional groups include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, and benzoguanamine derivatives, blocked isocyanate compounds, cyclocarbonate compounds, and cyclic (thio) ether groups. A known thermosetting resin such as a thermosetting component, bismaleimide, or carbodiimide resin can be used. Particularly preferred are blocked isocyanate compounds from the viewpoint of excellent storage stability.

Among the above, the thermosetting compound having a plurality of cyclic (thio) ether groups in the molecule includes either one of the three, four, or five-membered cyclic (thio) ether groups or a plurality of two types of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and having a plurality of thioether groups in the molecule Examples thereof include compounds, that is, episulfide resins.

Examples of the polyfunctional epoxy compound include epoxidized vegetable oils such as Adekasizer O-130P, Adekasizer O-180A, Adekasizer D-32, and Adekasizer D-55 manufactured by ADEKA; jER828, jER834 manufactured by Mitsubishi Chemical Corporation; jER1001, jER1004, DIC's Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Etototo YD-011, YD-013, YD-127, YD-128, Dow Chemical Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resins such as 664 (all trade names); hydroquinone type epoxy resins such as YDC-1312; bisphenol type epoxy resins such as YSLV-80XY; thioether type epoxy resins such as YSLV-120TE (all are Toto Kasei Co., Ltd.) JERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152 and Epicron 165 manufactured by DIC, Epototo YDB-400 and YDB-500 manufactured by Tohto Kasei Co., Ltd., and D.C. E. R. 542, Sumitomo Epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd. 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, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235 and ECN-299 (both trade names); biphenol novolak type epoxy resins such as NC-3000 and NC-3100 manufactured by Nippon Kayaku; Epicron 830 manufactured by DIC, Mitsubishi Chemical JER807 manufactured by Toto Kasei Co., Ltd. Etototo YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F type epoxy resin; Toto Kasei Co., Ltd. Epototo ST-2004, ST-2007, ST Hydrogenated bisphenol A type epoxy resin such as -3000 (trade name); jER604 manufactured by Mitsubishi Chemical Corporation, Epotot YH-434 manufactured by Tohto Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy Resin; manufactured by Mitsubishi Chemical Corporation of YL-933, manufactured by Dow Chemical Company of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names), etc. Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name), etc .; bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) manufactured by Mitsubishi Chemical; TEPIC manufactured by Nissan Chemical Industries (all) Product name) heterocyclic epoxy resin; Jig such as Bremer DGT manufactured by NOF Corporation Cisyl phthalate resin; Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tohto Kasei; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd. HP-4032, EXA-4750, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; Further, copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivatives, CTBN-modified epoxy resins (for example, YR-102, YR-450, etc. manufactured by Tohto Kasei Co., Ltd.), etc. are limited thereto. It is not a thing. These epoxy resins can be used alone or in combination of two or more. Among these, novolak-type epoxy resins, bixylenol-type epoxy resins, biphenol-type epoxy resins, biphenol novolac-type epoxy resins, naphthalene-type epoxy resins or mixtures thereof are particularly preferable.

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

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. 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.

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

Examples of these commercially available products include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156. 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Mitsui Cyanamid), 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 (all manufactured by Sanwa Chemical Co., Ltd.).

An isocyanate compound and a blocked isocyanate compound are compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule. Examples of such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule include polyisocyanate compounds or blocked isocyanate compounds. The blocked isocyanate group is a group in which the isocyanate group is protected by the reaction with the blocking agent and temporarily inactivated, and the blocking agent is dissociated when heated to a predetermined temperature. Produces. It was confirmed that the curability and the toughness of the resulting cured product were improved by adding the polyisocyanate compound or the blocked isocyanate compound.

As such a polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.

Specific examples of the aromatic polyisocyanate include, for example, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and m-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, the adduct body, burette body, isocyanurate body, etc. of the isocyanate compound mentioned above are mentioned.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. As an isocyanate compound which can react with a blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example.

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

The blocked isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (all manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate 2512, Coronate 2513, Coronate 2520 (all manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals), and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent. Such a compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule may be used alone or in combination of two or more.

(C) The blending ratio of the thermosetting compound is preferably in the range of 10 to 70 parts by mass and more preferably in the range of 20 to 60 parts by mass in 100 parts by mass of the curable composition of the present invention. When the blending amount is 10 parts by mass or more, sufficient toughness and heat resistance of the coating film can be obtained. On the other hand, if it is 70 mass parts or less, it can suppress that storage stability falls. (C) A thermosetting compound may be used individually by 1 type, and may be used in combination of 2 or more type.

[(D) Epoxy (meth) acrylate resin having at least one (meth) acryloyl group]
Examples of the epoxy (meth) acrylate resin having at least one (meth) acryloyl group include bisphenol A type epoxy (meth) acrylate resin, bisphenol F type epoxy (meth) acrylate resin, bisphenol E type epoxy (meth) acrylate resin, and cresol. Examples include novolac type epoxy (meth) acrylate resins, phenol novolac type epoxy (meth) acrylate resins, and aliphatic epoxy (meth) acrylates.

As bisphenol A type epoxy (meth) acrylate resins, EBECRYL 600, EBECRYL 605, EBECRYL 648, EBECRYL 3700, EBECRYL 3703 (above trade names of Daicel Ornex Co., Ltd.), epoxy ester EX-0205, epoxy ester 3000A, epoxy ester 3002A (Non-trade name, manufactured by Kyoei Chemical Co., Ltd.), 8026, 8101, 8125, 8197, 8250 L MH, 8260, 8355, 8360BR, 8327, 8351 (trade names manufactured by Japan Eupika Co., Ltd.) (Product name manufactured by Hitachi Chemical Co., Ltd.), Biscote # 540 (Product name manufactured by Osaka Organic Chemical Industry Co., Ltd.), CN104, CN104A80, CN104B80, CN120, CN12 A60, CN120A75, CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN120E50, CN120M50, CN151 (or trade names manufactured by Sartomer), Miramer PE210 (or product names manufactured by Toyo Chemicals), NK Oligo EA-10 1010LC, EA-1010NT, EA-1020, EA-1020LC3, EMA-1020 (trade names manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

Examples of the bisphenol F-type epoxy (meth) acrylate resin include 8475, 8476 (trade names manufactured by Nippon Iupika Co., Ltd.) and the like. *

Examples of the cresol novolac type epoxy (meth) acrylate resin include NK oligos EA-7120 / PGMAC, EA-7140 / PGMAC, EA-7420 / PGMAC (trade names manufactured by Shin-Nakamura Chemical Co., Ltd.).

Phenol novolac type epoxy (meth) acrylate resins include 8400, 8411, L H (trade name, manufactured by Nippon Iupika Co., Ltd.), Hitaroid 7663 (trade name, manufactured by Hitachi Chemical Co., Ltd.), NK Oligo EA-6320 / PGMAC, EA- 6340 / PGMAC (trade name manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of the aliphatic epoxy (meth) acrylate include EBECRYL 3500, EBECRYL 3608, EBECRYL 3702 (above, trade names made by Daicel Ornex), Miramer PE230 (trade names made by Toyo Chemicals), and the like.

Among the above epoxy (meth) acrylate resins, bisphenol A type epoxy (meth) acrylate resins, bisphenol F type epoxy (meth) acrylate resins, and bisphenol E type epoxy (meth) acrylate resins having a relatively low viscosity and excellent heat resistance. Bisphenol type epoxy (meth) acrylate resins such as are preferred.

The viscosity of the epoxy (meth) acrylate resin at 40 ° C. is preferably in the range of 100 to 40,000 mPa · s. The blending ratio of the epoxy (meth) acrylate resin is preferably in the range of 5 to 50 parts by mass and more preferably in the range of 10 to 35 parts by mass in 100 parts by mass of the curable composition of the present invention. When the compounding amount of the epoxy (meth) acrylate resin is 5 parts by mass or more, the effect of improving the gold plating resistance is obtained, and when it is 50 parts by mass or less, the compatibility is improved and the coating is uniformly dispersed, and a good coating film Characteristics are obtained. An epoxy (meth) acrylate resin may be used individually by 1 type, and may be used in combination of 2 or more type.

[(E) Bifunctional (meth) acrylate compound]
The curable composition of the present invention may further contain (E) a bifunctional (meth) acrylate compound. (E) A bifunctional (meth) acrylate compound is preferable because it is used as a reactive diluent and has a good balance between dilution effect and heat resistance. (E) The viscosity of a curable composition can be reduced by mix | blending a bifunctional (meth) acrylate compound. Specific examples of the bifunctional (meth) acrylate compound include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, and the like. Diacrylate diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl Glycol diacrylate, neopentyl glycol, at least one of ethylene oxide and propylene oxide Diacrylate of diol obtained by adding seed, diacrylate of glycol such as caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, bisphenol A EO adduct diacrylate, bisphenol APO adduct diacrylate, bisphenol A diglycidyl ether acrylic Diacrylate of diol obtained by adding at least one of ethylene oxide and propylene oxide to acid addition product, tricyclodecane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanurate bisphenol A, hydrogenated dicyclo Diacrylates having a cyclic structure such as pentadienyl diacrylate and cyclohexyl diacrylate, isocyanuric acid ethylene oxide modified diacrylate Such as diacrylate isocyanuric acid.

Commercially available products include light acrylate 1,6HX-A, 1,9ND-A, 3EG-A, 4EG-A (trade names manufactured by Kyoeisha Chemical Co., Ltd.), HDDA, 1,9-NDA, DPGDA, TPGDA (Daicel Product name manufactured by Ornex Co., Ltd.), Biscote # 195, # 230, # 230D, # 260, # 310HP, # 335HP, # 700HV, # 540 (trade names manufactured by Osaka Organic Chemical Industry Co., Ltd.), Aronix M-208, M -211B, M-215, M-220, M-225, M-240, M-270 (trade names manufactured by Toagosei Co., Ltd.) and the like.

Among the bifunctional (meth) acrylates, a diacrylate of a diol having an alkylene chain is preferable from the viewpoint of viscosity and compatibility. Among these, diacrylates of diols having an alkylene chain having 4 to 12 carbon atoms are more preferable. Examples include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, and the like.

In addition, the blending ratio of the (E) bifunctional (meth) acrylate compound is preferably in the range of 10 to 80 parts by mass and more preferably in the range of 30 to 60 parts by mass in 100 parts by mass of the curable composition of the present invention. (E) When the blending amount of the bifunctional (meth) acrylate compound is 10 parts by mass or more, the compatibility is improved, the dispersion is uniformly dispersed, and good coating properties are obtained. The effect of improving the properties can be obtained. (E) A bifunctional (meth) acrylate compound may be used individually by 1 type, and may be used in combination of 2 or more type.

In the curable composition of the present invention, a reactive diluent other than the (E) bifunctional (meth) acrylate compound can be further blended. By mix | blending a reactive diluent, the viscosity of a curable composition can be reduced. Examples of other reactive diluents include photoreactive diluents and heat reactive diluents. Among these, a photoreactive diluent is preferable.

Photoreactive diluents include (meth) acrylates, vinyl ethers, ethylene derivatives, styrene, chloromethylstyrene, α-methylstyrene, maleic anhydride, dicyclopentadiene, N-vinylpyrrolidone, N-vinylformamide, xylyl Examples thereof include compounds having an unsaturated double bond, oxetanyl group, and epoxy group, such as range oxetane, oxetane alcohol, 3-ethyl-3- (phenoxymethyl) oxetane, resorcinol diglycidyl ether, and the like.

Among these, (meth) acrylates are preferable, and (meth) acrylates include those other than the above (E) bifunctional (meth) acrylate compounds, such as monofunctional (meth) acrylate compounds, trifunctional (meth) acrylates. A compound or the like can be used.

Examples of the monofunctional (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2- Examples include (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, and acryloylmorpholine. Specific examples of the trifunctional (meth) acrylate compounds include trifunctional acrylates such as trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane PO-modified triacrylate, trimethylolpropane EO-modified triacrylate, and trifunctional polyester acrylate. Is mentioned.

The mixing ratio of these other reactive diluents is preferably in the range of 1 to 70 parts by mass, more preferably in the range of 5 to 60 parts by mass, in 100 parts by mass of the curable composition of the present invention. When the blending amount of other reactive diluents is 1 part by mass or more, the compatibility is improved, the dispersion is uniformly dispersed, and good coating properties are obtained. Is obtained. A reactive diluent may be used individually by 1 type, and may be used in combination of 2 or more type.

In the curable composition of the present invention, the amount of the monofunctional reactive diluent is preferably as small as possible, specifically 10 parts by mass or less in 100 parts by mass of the curable composition of the present invention. Is preferred. When the blending amount of the monofunctional reactive diluent is small, the crosslink density increases, and the properties such as solder heat resistance become better.

A thermosetting catalyst can be further blended in the curable composition of the present invention. The thermosetting catalyst is used to further improve the thermosetting properties of the (C) thermosetting compound, for example, amine compounds such as dicyandiamide and aromatic amines, imidazoles, phosphorus compounds, acid anhydrides, bicyclics Amidine compounds can be used. Specifically, imidazole, 1-benzyl-2-phenylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2 -Imidazoles such as phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy- Amine compounds such as N, N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine, phosphorus compounds such as triphenylphosphine, and the like can be used. More specifically, as imidazole compounds, 1B2PZ, 2E4MZ, 2MZ-A, 2MZ-OK, 2PHZ, 2P4MHZ (manufactured by Shikoku Kasei Kogyo Co., Ltd.); dimethylamine as a blocked isocyanate compound, U-CAT3503N, −3502T (Manufactured by San Apro); Examples of bicyclic amidine compounds and salts thereof include DBU, DBN, U-CATＣSA102, U-CAT 5002 (manufactured by San Apro). These may be used singly or in combination of two or more.

For the content of the thermosetting catalyst, a normal blending ratio is sufficient. For example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the (C) thermosetting compound is preferable.

In addition to the above components, the curable composition of the present invention includes, as necessary, a surface tension adjuster, a surfactant, a matting agent, a polyester resin, a polyurethane resin, and a vinyl resin for adjusting film physical properties. , Acrylic resins, rubber resins, waxes, commonly known colorants such as red, blue, green, yellow, white and black, such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet , Titanium oxide, carbon black, naphthalene black, silicone, fluorine, polymer, etc., antifoaming agent and leveling agent, imidazole, thiazole, triazole, silane coupling agent, etc. Known and commonly used additives such as an imparting agent can be blended.

The curable composition of the present invention having the above components is used in an ink jet printing method. From this point, the curable composition of the present invention preferably has a viscosity at 50 ° C. of 50 mPa · s or less, particularly 10 to 30 mPa · s. Thereby, smooth printing can be performed without applying an unnecessary load to the ink jet printer. Moreover, the viscosity at normal temperature of the curable composition of this invention is 150 mPa * s or less suitably, and the printing by an inkjet printing method is performed favorably by this. Here, in this invention, a viscosity means the viscosity measured at normal temperature (25 degreeC) or 50 degreeC according to JISK2283.

Moreover, the curable composition of the present invention can be printed on a flexible wiring board by a roll-to-roll method. In this case, it is possible to form a resist pattern at a high speed by attaching a light irradiation light source to be described later after passing through the ink jet printer.

The light irradiation is performed by irradiation with ultraviolet rays or active energy, but ultraviolet rays are preferable. As a light source for light irradiation, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, an LED lamp having a wavelength in the ultraviolet region such as 365, 385, 395, and 405 nm is suitable. In addition, electron beams, α rays, β rays, γ rays, X rays, neutron rays, and the like can also be used. Further, if necessary, it is cured by heating after light irradiation. Here, the heating temperature is, for example, 80 to 200 ° C. By setting this heating temperature range, it can be sufficiently cured. The heating time is, for example, 10 to 100 minutes.

By applying at least one or both of light irradiation and heating as described above to a coating film obtained by printing the curable composition of the present invention by an ink jet method, a high hardness cured coating film is obtained. be able to. The curable composition of the present invention is capable of forming a cured pattern coating film having excellent properties such as solder heat resistance, gold plating resistance, pencil hardness, chemical resistance, and bendability as well as excellent adhesion to the substrate. is there.

The curable composition of the present invention can be suitably used as a permanent insulating film, for example, a solder resist for printed wiring boards. Moreover, the printed wiring board of this invention has the characteristics in having the cured coating film formed using the said curable composition of this invention on a board | substrate.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples.

According to the formulation described in Table 1 below, the materials described in Examples and Comparative Examples were respectively mixed and premixed with a stirrer to prepare a curable composition. In addition, unless otherwise indicated, the value of the compounding amount in a table | surface shows the mass part of solid content.

＊１－１）ＵＡ－４２００、新中村化学工業社製、２官能ポリエーテルウレタンアクリレート，２５℃における粘度２，０００ｍＰａ・ｓ
＊１－２）ＤＭ５７６、ＤＯＵＢＬＥ　ＢＯＮＤ　ＣＨＥＭＩＣＡＬ社製、脂肪族６官能ウレタンアクリレートオリゴマー，２５℃における粘度１，０００－３，０００ｍＰａ・ｓ
＊１－３）ＤＭ７７６、ＤＯＵＢＬＥ　ＢＯＮＤ　ＣＨＥＭＩＣＡＬ社製、芳香族６官能ウレタンアクリレートオリゴマー，２５℃における粘度４，０００－６，０００ｍＰａ・ｓ
＊１－４）ダロキュア１１７３、ＢＡＳＦジャパン社製，２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン，　
＊１－５）イルガキュア８１９、ＢＡＳＦジャパン社製，ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（ビスアシルフォスフィンオキサイド系）
＊１－６）ＢＩ７９８２，Ｂａｘｅｎｄｅｎ　Ｃｈｅｍｉｃａｌ社製、３官能ブロックイソシアネート
＊１－７）４ＨＢＡ、日本化成社製、４－ヒドロキシブチルアクリレート
＊１－８）ＥＡ－１０１０Ｎ、新中村化学工業社製、（メタ）アクリロイル基含有ビスフェノールＡ型エポキシ樹脂（単官能）、４０℃における粘度１０，０００～３０，０００ｍＰａ・ｓ
＊１－９）Ａ－ＮＯＤ－Ｎ、新中村化学工業社製、１，９－ノナンジオールジアクリレート（２官能アクリレートモノマー）
＊１－１０）ファストゲンブルー５３８０、ＤＩＣ社製、フタロシアニンブルー（顔料）
＊１－１１）クロモフタルエローＡＧＲ、ＢＡＳＦジャパン社製、クロモフタルエロー（顔料）

* 1-1) UA-4200, manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional polyether urethane acrylate, viscosity at 25 ° C. 2,000 mPa · s
* 1-2) DM576, manufactured by DOUBLE BOND CHEMICAL, aliphatic hexafunctional urethane acrylate oligomer, viscosity at 25 ° C., 1,000-3,000 mPa · s
* 1-3) DM776, manufactured by DOUBLE BOND CHEMICAL, aromatic hexafunctional urethane acrylate oligomer, viscosity at 25 ° C., 4,000-6,000 mPa · s
* 1-4) Darocur 1173, manufactured by BASF Japan, 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
* 1-5) Irgacure 819, manufactured by BASF Japan, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (bisacylphosphine oxide type)
* 1-6) BI7982, manufactured by Baxen Chemical, trifunctional blocked isocyanate * 1-7) 4HBA, manufactured by Nippon Kasei Co., Ltd., 4-hydroxybutyl acrylate * 1-8) EA-1010N, manufactured by Shin-Nakamura Chemical Co., Ltd. ( (Meth) acryloyl group-containing bisphenol A type epoxy resin (monofunctional), viscosity at 40 ° C. 10,000 to 30,000 mPa · s
* 1-9) A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd., 1,9-nonanediol diacrylate (bifunctional acrylate monomer)
* 1-10) Fast Gen Blue 5380, manufactured by DIC, Phthalocyanine Blue (pigment)
* 1-11) Chromophthalo Yellow AGR, manufactured by BASF Japan, Chromophthalo Yellow (pigment)

The curable compositions of the obtained Examples and Comparative Examples were evaluated according to the following. The results are shown in Table 2 below.

(1) Viscosity at 50 ° C. Viscosity of the curable compositions obtained in each Example and Comparative Example at an ink temperature of 50 ° C. and 100 rpm was measured with a cone plate viscometer (TVH-33H manufactured by Toki Sangyo Co., Ltd.). . The results were evaluated based on the following criteria.
○: More than 10 mPa · s and 50 mPa · s or less.
Δ: More than 50 mPa · s and 200 mPa · s or less.
X: Over 200 mPa · s.

(2) Adhesion test The curable compositions obtained in Examples 1-1 to 1-6 and the comparative examples were applied on a copper clad laminate using a 30 μm applicator (manufactured by ERICHSEN), and a high-pressure mercury lamp ( Curing was performed at 150 mJ / cm ² with HMW-713) manufactured by ORC. For Example 1-7, the curable composition was applied by inkjet onto a copper clad laminate using a material printer DMP-2831 manufactured by Fuji Global Graphic Systems, and 150 mJ / cm ² with an LED lamp (ANUJ6164 manufactured by Panasonic). And cured. Thereafter, heat treatment was performed for 60 minutes in a hot air circulation drying furnace at 150 ° C. A cross-cut tape peel test was performed on the prepared sample. The results were evaluated based on the following criteria by counting how many of the 100 remaining grids were present.
A: 100/100.
○: 80 to 99/100.
Δ: 60-79 / 100.
X: 59 or less / 100.

(3) Pencil hardness (surface hardness)
The pencil hardness on the surface was measured in accordance with JIS K 5600-5-4 using the cured coating films of the examples and comparative examples obtained under the substrate preparation conditions of (2) above.

(4) Solder heat resistance Applying rosin-based flux to the cured coating films of the examples and comparative examples obtained under the substrate preparation conditions of (2) above, and immersing in a solder bath at 260 ° C. for 10 seconds 3 times After repetition, a cross-cut tape peel test was performed. The results were evaluated based on the following criteria by counting how many of the 100 remaining grids were present.
A: 100/100.
○: 80 to 99/100.
Δ: 60-79 / 100.
X: 59 or less / 100.

(5) Resistance to gold plating Using commercially available electroless nickel plating bath and electroless gold plating bath for the cured coating film of each of the examples and comparative examples obtained under the substrate preparation conditions of (2) above, nickel 0. Plating was performed under conditions of 5 μm and gold 0.03 μm, and a cross-cut tape peel test was performed. The results were evaluated based on the following criteria by counting how many of the 100 remaining grids were present.
A: 100/100.
○: 80 to 99/100.
Δ: 60-79 / 100.
X: 59 or less / 100.

As shown in the above table, each of the curable compositions of Examples including a urethane (meth) acrylate resin having a predetermined functional number and a photopolymerization initiator is in addition to solder heat resistance and gold plating resistance. Thus, it was confirmed that it had good adhesion on the substrate, had a high hardness after curing, and had a low viscosity suitable for inkjet printing.

In Examples 1-1 to 1-4, a curable composition having a low viscosity and a high hardness can be obtained by using a polyfunctional, low-viscosity aliphatic hexafunctional urethane acrylate oligomer as the urethane (meth) acrylate resin. It turns out that it is obtained. Also in Examples 1-5 to 1-7, in which a polyfunctional, low-viscosity aromatic hexafunctional urethane acrylate oligomer is used as the urethane (meth) acrylate resin, curability with low viscosity and high hardness is also obtained. A composition has been obtained.

On the other hand, Comparative Example 1-1 which does not contain urethane (meth) acrylate resin is inferior in solder heat resistance and gold plating resistance. In Comparative Examples 1-2 to 1-4 that do not contain a thermosetting compound, the solder heat resistance and gold plating resistance are further reduced, the adhesion is deteriorated, and no comparison is made with no bifunctional acrylate monomer. In Example 1-4, the viscosity was high and it was not suitable for inkjet printing.

According to the formulation described in Table 3 below, the materials described in Examples and Comparative Examples were respectively mixed and premixed with a stirrer to prepare a curable composition. In addition, unless otherwise indicated, the value of the compounding amount in a table | surface shows the mass part of solid content.

＊２－１）ＵＡ－４２００、新中村化学工業社製、２官能ポリエーテルウレタンアクリレート，２５℃における粘度２，０００ｍＰａ・ｓ
＊２－２）ＤＭ５７６、ＤＯＵＢＬＥ　ＢＯＮＤ　ＣＨＥＭＩＣＡＬ社製、脂肪族６官能ウレタンアクリレートオリゴマー，２５℃における粘度１，０００－３，０００ｍＰａ・ｓ
＊２－３）ＤＭ７７６、ＤＯＵＢＬＥ　ＢＯＮＤ　ＣＨＥＭＩＣＡＬ社製、芳香族６官能ウレタンアクリレートオリゴマー，２５℃における粘度４，０００－６，０００ｍＰａ・ｓ
＊２－４）ダロキュア１１７３、ＢＡＳＦジャパン社製、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン，　
＊２－５）イルガキュア８１９、ＢＡＳＦジャパン社製、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（ビスアシルフォスフィンオキサイド系）
＊２－６）Ａ－ＮＯＤ－Ｎ、新中村化学工業社製、１，９－ノナンジオールジアクリレート（２官能アクリレートモノマー）
＊２－７）ＥＡ－１０１０Ｎ、新中村化学工業社製、（メタ）アクリロイル基含有ビスフェノールＡ型エポキシ樹脂（単官能），４０℃における粘度１０，０００～３０，０００ｍＰａ・ｓ
＊２－８）３００２Ａ（Ｎ）、ケーエスエム社製，ＰＯ変性ビスフェノールＡ型エポキシアクリレート（ビスフェノールＡ　ＰＯ２ｍｏｌ付加物、ジグリシジルエーテル　アクリル酸付加物）
＊２－９）４ＨＢＡ、日本化成社製、４－ヒドロキシブチルアクリレート
＊２－１０）ＢＩ７９８２、Ｂａｘｅｎｄｅｎ社製、３官能ブロックイソシアネート
＊２－１１）ファストゲンブルー５３８０、ＤＩＣ社製、フタロシアニンブルー（顔料）
＊２－１２）クロモフタルエローＡＧＲ、ＢＡＳＦジャパン社製、クロモフタルエロー（顔料）

* 2-1) UA-4200, manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional polyether urethane acrylate, viscosity at 25 ° C. 2,000 mPa · s
* 2-2) DM576, manufactured by DOUBLE BOND CHEMICAL, aliphatic hexafunctional urethane acrylate oligomer, viscosity at 25 ° C. 1,000-3,000 mPa · s
* 2-3) DM776, manufactured by DOUBLE BOND CHEMICAL, aromatic hexafunctional urethane acrylate oligomer, viscosity at 25 ° C., 4,000 to 6,000 mPa · s
* 2-4) Darocur 1173, manufactured by BASF Japan, 2-hydroxy-2-methyl-1-phenyl-propan-1-one,
* 2-5) Irgacure 819, manufactured by BASF Japan, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (bisacylphosphine oxide)
* 2-6) A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd., 1,9-nonanediol diacrylate (bifunctional acrylate monomer)
* 2-7) EA-1010N, manufactured by Shin-Nakamura Chemical Co., Ltd., (meth) acryloyl group-containing bisphenol A type epoxy resin (monofunctional), viscosity at 40 ° C., 10,000 to 30,000 mPa · s
* 2-8) 3002A (N), manufactured by KSM Co., Ltd., PO-modified bisphenol A type epoxy acrylate (bisphenol A PO 2 mol adduct, diglycidyl ether acrylic acid adduct)
* 2-9) 4HBA, Nippon Kasei Co., Ltd., 4-hydroxybutyl acrylate * 2-10) BI7982, Baxenden, trifunctional block isocyanate * 2-11) Fastgen Blue 5380, DIC, Phthalocyanine Blue (pigment) )
* 2-12) Chromophthalo Yellow AGR, manufactured by BASF Japan, Chromophthalo Yellow (pigment)

The curable compositions of the obtained Examples and Comparative Examples were evaluated according to the following. The results are shown in Table 4 below.

(1) Viscosity at 50 ° C. Viscosity of the curable compositions obtained in each Example and Comparative Example at an ink temperature of 50 ° C. and 100 rpm was measured with a cone plate viscometer (TVH-33H manufactured by Toki Sangyo Co., Ltd.). . The results were evaluated based on the following criteria.
○: More than 10 mPa · s and 50 mPa · s or less.
Δ: More than 50 mPa · s and 200 mPa · s or less.
X: Over 200 mPa · s.

(2) Adhesion test The curable compositions obtained in Examples 2-1 to 2-7 and the comparative example were applied onto a copper clad laminate using a 30 μm applicator (manufactured by ERICHSEN), and a high-pressure mercury lamp ( Curing was performed at 150 mJ / cm ² with HMW-713) manufactured by ORC. For Example 2-8, the curable composition was applied by inkjet onto a copper clad laminate using a material printer DMP-2831 manufactured by Fuji Global Graphic Systems, and 150 mJ / cm ² with an LED lamp (ANUJ6164 manufactured by Panasonic). And cured. Thereafter, heat treatment was performed for 60 minutes in a hot air circulation drying furnace at 150 ° C. A cross-cut tape peel test was performed on the prepared sample. The results were evaluated based on the following criteria by counting how many of the 100 remaining grids were present.
A: 100/100.
○: 80 to 99/100.
Δ: 60-79 / 100.
X: 59 or less / 100.

(3) Pencil hardness (surface hardness)
The pencil hardness on the surface was measured in accordance with JIS K 5600-5-4 using the cured coating films of the examples and comparative examples obtained under the substrate preparation conditions of (2) above.

(4) Solder heat resistance Applying rosin-based flux to the cured coating films of the examples and comparative examples obtained under the substrate preparation conditions of (2) above, and immersing in a solder bath at 260 ° C. for 10 seconds 3 times After repetition, a cross-cut tape peel test was performed. The results were evaluated based on the following criteria by counting how many of the 100 remaining grids were present.
A: 100/100.
○: 80 to 99/100.
Δ: 60-79 / 100.
X: 59 or less / 100.

(5) Resistance to gold plating Using commercially available electroless nickel plating bath and electroless gold plating bath for the cured coating film of each of the examples and comparative examples obtained under the substrate preparation conditions of (2) above, nickel 0. Plating was performed under conditions of 5 μm and gold 0.03 μm, and a cross-cut tape peel test was performed. The results were evaluated based on the following criteria by counting how many of the 100 remaining grids were present.
A: 100/100.
○: 80 to 99/100.
Δ: 60-79 / 100.
X: 59 or less / 100.

As shown in the above table, each of the curable compositions of Examples including a urethane (meth) acrylate resin having a predetermined functional number and a photopolymerization initiator is in addition to solder heat resistance and gold plating resistance. Thus, it was confirmed that it had good adhesion on the substrate, had a high hardness after curing, and had a low viscosity suitable for inkjet printing.

In Examples 2-1 to 2-4, a polyfunctional, low-viscosity aliphatic hexafunctional urethane acrylate oligomer is used as the urethane (meth) acrylate resin, so that a curable composition having a low viscosity and a high hardness can be obtained. Although it is obtained, it can be seen that when the amount of the urethane (meth) acrylate resin is too large as in Example 2-5, the viscosity increases. Further, in Examples 2-6 to 2-8 in which a polyfunctional, low-viscosity aromatic hexafunctional urethane acrylate oligomer is used as the urethane (meth) acrylate resin, the curability having low viscosity and high hardness is also obtained. A composition has been obtained.

On the other hand, Comparative Example 2-1 that does not contain a urethane (meth) acrylate resin and Comparative Example 2-2 that does not contain an epoxy (meth) acrylate resin have poor solder heat resistance and gold plating resistance. In Comparative Example 2-3 that did not contain a bifunctional acrylate monomer, the viscosity was high and it was not suitable for inkjet printing.

Claims (11)

(A) a urethane (meth) acrylate resin having 5 to 12 functional groups;
(B) a photopolymerization initiator;
A curable composition for inkjet, comprising: 2. The curable composition for inkjet according to claim 1, wherein the viscosity of the (A) urethane (meth) acrylate resin at 25 ° C. is 1,000 to 20,000 mPa · s. 2. The composition further comprises (C) a thermosetting compound having at least one heat-reactive functional group (excluding an epoxy (meth) acrylate resin having at least one (meth) acryloyl group). A curable composition for inkjet. As the (C) thermosetting compound (excluding an epoxy (meth) acrylate resin having at least one (meth) acryloyl group), a compound having at least one (meth) acryloyl group and at least one thermoreactive functional group is used. The curable composition for inkjet according to claim 3, comprising 1 thermosetting compound and a second thermosetting compound having at least two thermoreactive functional groups. 2. The curable composition for inkjet according to claim 1, further comprising (D) an epoxy (meth) acrylate resin having at least one (meth) acryloyl group. 6. The curable composition for inkjet according to claim 5, wherein the (D) epoxy (meth) acrylate resin is a bisphenol type epoxy (meth) acrylate resin. The curable composition for inkjet according to claim 1, further comprising (E) a bifunctional (meth) acrylate compound. The curable composition for inkjet according to claim 7, wherein the (E) bifunctional (meth) acrylate compound is a compound having an alkylene chain having 4 to 12 carbon atoms. The curable composition for inkjet according to claim 1, wherein the viscosity at 50 ° C. is 50 mPa · s or less. A cured coating film obtained by curing the curable composition for inkjet according to claim 1. A printed wiring board comprising the cured coating film according to claim 10 on a substrate.