TW201726841A - 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, hardened coating film using the same, and printed circuit board

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

In recent years, as a method of forming an etching resist, a solder resist, a symbol mark, or the like on a coating film on a printed wiring board, a printing method using an inkjet method has been attracting attention from the viewpoint of simplicity (Patent Document 1).

[Previous Technical Literature] [Patent Document]

Patent Document 1: International Publication No. 2004/099272

On the other hand, for various curable compositions for printed circuit boards such as resist ink or marking ink formed on a printed circuit board, it is required to have a base such as a conductor layer of a conductive circuit metal or a plastic substrate. Good adhesion, high hardness after hardening, and solder heat resistance or gold plating resistance under severe conditions.

However, the composition for printing by the ink jet method is difficult to satisfy the printability (coatability) of the ink jet method, and it is difficult to fully satisfy the required performance as described above.

Accordingly, it is an object of the present invention to provide a good adhesion to a substrate in addition to solder heat resistance, gold plating resistance, etc., high hardness after hardening, and low viscosity suitable for ink jet printing. A curable composition for inkjet, a cured coating film using the same, and a printed circuit board.

As a result of a review by the inventors of the present invention, it has been found that the above problems can be solved by a curable composition containing a specific functional number of urethane (meth) acrylate resin and a photopolymerization initiator, thereby completing the present invention. .

In other words, the curable composition for inkjet according to the present invention is characterized by containing (A) a 5- or more-functional 12-functional urethane (meth) acrylate resin and (B) a photopolymerization initiator. .

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. Moreover, the curable composition of the present invention is better One step contains (C) a thermosetting compound having at least one thermally reactive functional group (excluding an epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group) as the aforementioned (C) thermosetting property The compound (excluding the epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group) preferably contains the first thermosetting having at least one (meth) acryl fluorenyl group and at least one thermally reactive functional group a compound and a second thermosetting compound having at least two thermally reactive functional groups. Further, the curable composition of the present invention preferably further contains (D) an epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group, and the above (D) epoxy (meth) acrylate. The resin is preferably a bisphenol type epoxy (meth) acrylate resin. Further, the curable composition of the present invention preferably further contains (E) a bifunctional (meth) acrylate compound, and the (E) bifunctional (meth) acrylate compound preferably has a carbon number of 4~ A compound of 12 alkyl chain. Further, the curable composition of the present invention preferably has a viscosity of 50 mPa at 50 ° C. s below.

The cured coating film of the present invention is characterized in that the curable composition for inkjet according to the present invention is cured.

The printed circuit board of the present invention is characterized in that it has the above-mentioned hard coat film of the present invention on a substrate.

According to the present invention, in addition to the properties of solder heat resistance or gold plating resistance, etc., it also has good adhesion to the substrate, high hardness after hardening, and low viscosity suitable for inkjet printing. A curable composition for inkjet, a cured coating film using the same, and a printed circuit board.

Hereinafter, embodiments of the present invention will be described in detail.

Further, in the present invention, the term "hard composition" means a composition which is hardened by light, heat or both. Further, the term "(meth)acrylate" acrylate, methacrylate, and the like are collectively the same as the other similar surfaces.

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

[(A) 5-functional or higher 12-functional urethane (meth) acrylate resin]

The (A) urethane (meth) acrylate resin is a compound having a complex urethane bond and a plurality of (meth) acryl oxime groups. The 5-functional urethane (meth) acrylate resin which can be used in the present invention is DM850 manufactured by DOUBLE BOND CHEMICAL Co., Ltd., HITALOID 7903-1 manufactured by Hitachi Chemical Co., Ltd., and the like. Further, as the hexafunctional urethane (meth) acrylate resin, U-6LPA, UA-1100H manufactured by Shin-Nakamura Chemical Co., Ltd., CN975 manufactured by SATOMER Co., Ltd., EBECRYL 220, KRM8200AE manufactured by DAICEL ALLNEX Co., Ltd. , EBECRYL 8254, EBECRYL 8301R, DOUBLE BOND CHEMICAL company DM527, DM528, DM571, DM576, DM776, DM87A, DM88A, HITALOID 7902-1, TA24-195H, etc. manufactured by Hitachi Chemical Co., Ltd.

Further, as the hexafunctional urethane (meth) acrylate resin, KRM8904 manufactured by DAICEL ALLNEX Co., Ltd., HITALOID 7903-3, HITALOID 7903-B manufactured by Hitachi Chemical Co., Ltd., and the like are exemplified. Further, examples of the 10-functional urethane (meth) acrylate resin include KRM8452 manufactured by DAICEL ALLNEX Co., Ltd., DM588 manufactured by DOUBLE BOND CHEMICAL Co., Ltd., and the like. Further, as the 12-functional urethane (meth) acrylate resin, DM5812 manufactured by DOUBLE BOND CHEMICAL Co., Ltd., HITALOID 7903-4 manufactured by Hitachi Chemical Co., Ltd., and the like are exemplified. These urethane (meth) acrylate resins may be used singly or as a mixture of two or more kinds.

In order to suppress the viscosity of the entire composition to a low level, the viscosity of the (A) urethane (meth) acrylate resin at 25 ° C is preferably from 1,000 to 20,000 mPa. s, especially preferably 1,000 to 10,000 mPa. s. By using a relatively low-viscosity (A) urethane (meth) acrylate resin to suppress the viscosity of the entire composition to a low level, the ejection property and stability at the time of inkjet printing can be improved. By using a 5-functional or higher urethane (meth) acrylate resin, heat resistance is provided, and by using a 12-functional or less urethane (meth) acrylate resin, it can be formed. The coating film imparts flexibility and can improve characteristics such as adhesion. More preferably, it is 8 or less, and more preferably 6 or less.

(A) Modification of urethane (meth) acrylate resin The amount of the curable composition is preferably 0.5 to 60 parts by mass, more preferably 1.5 to 55 parts by mass, per 100 parts by mass of the curable composition. By setting the 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. In addition, when the amount of the urethane (meth) acrylate resin is 60 parts by mass or less, the viscosity of the curable composition can be suppressed to be low, and the ejection property at the time of inkjet printing can be satisfactorily ensured. . Stability.

[(B) Photopolymerization initiator]

The (B) photopolymerization initiator is not particularly limited, and for example, a photoradical polymerization initiator can be used. As the photoradical polymerization initiator, any compound which generates radicals by light, laser, electron beam or the like and initiates radical polymerization can be used.

The photoradical polymerization initiator is exemplified by benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ether, benzoin propyl ether; 2-hydroxy-2 -Alkylphenones such as methyl-1-phenylpropan-1-one, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Acetophenones such as 2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinepropane- Amines such as 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, N,N-dimethylaminoacetophenone, etc. Acetophenones; anthraquinones such as 2-methylindole, 2-ethylindole, 2-tert-butylindole, 1-chloroindole; 2,4-dimethylthioxanthone , 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.; acetophenone dimethyl ketal, benzyl dimethyl Ketal ketone Ketal; 2,4,5-triaryl imidazole dimer; riboflavin tetrabutyrate; 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, etc. Alcohol compound; organic halogen compound such as 2,4,6-tris-triazine, 2,2,2-tribromoethanol, tribromomethylphenylhydrazine; benzophenone, 4,4'-double Dibenzophenone or xanthone such as diethylaminobenzophenone; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethyl) A fluorenylphosphine oxide system such as a benzyl benzhydryl group-phenylphosphine oxide or the like.

These conventional photopolymerization initiators may be used singly or as a mixture of two or more kinds, and further, N,N-dimethylaminobenzoic acid ethyl ester and N,N-dimethylaminobenzoic acid may be added. A photoinitiator such as a tertiary amine such as amyl ester, amyl 4-dimethylaminobenzoate, triethylamine or triethanolamine.

Further, a ferrocene compound or the like of IRGACURE 784 (manufactured by BASF Corporation, Japan) having absorption in the visible light region may be added to promote photoreaction. It is not limited to this, and it is not limited to a photopolymerization initiator, light-emitting, as long as it absorbs ultraviolet light or visible light, and radically polymerizes an unsaturated group such as a (meth) acrylonitrile group. The starting agent can be used alone or in combination.

Commercially available, for example, IRGACURE 261, 184, 369, 651, 500, 819, 907, 784, 2959, IRGACURE 1116, 1173, IRGACURE TPO (all of which are trade names of Japan BASF Corporation), ESACURE KIP150, KIP65LT , KIP100F, KT37, KT55, KTO46, KIP75/B, ONE (trade name made by FRETELLI LAMBERTI).

(B) The blending ratio of the photopolymerization initiator is preferably from 1 to 25 parts by mass, more preferably from 5 to 20 parts by mass, particularly preferably from 5 parts by mass to 100 parts by mass of the curable composition of the present invention. ~15 parts by mass. By setting the blending ratio of the (B) photopolymerization initiator to the above range, appropriate photocurability can be obtained.

[(C) Thermosetting compound having at least one thermally reactive functional group (removing epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group)]

The thermoreactive functional group as the (C) thermosetting compound is derived from a hydroxyl group, a carboxyl group, an isocyanate group, an amine group, an imido group, an epoxy group, an oxetanyl group, a decyl group, a methoxymethyl group, or a methoxy group. Group selection of ethyl, ethoxymethyl, ethoxyethyl and oxazolinyl, cyclic (thio)ether, (cyclo)carbonate, cyclothio, polyoxazoline At least one of the conventional thermosetting functional groups, preferably from a hydroxyl group, a carboxyl group, an isocyanate group, an amine group, an imido group, an epoxy group, an oxetanyl group, a fluorenyl group, a methoxy group At least one functional group selected from the group consisting of a methoxy group, an ethoxymethyl group, an ethoxyethyl group, and an oxazolyl group.

The (C) thermosetting compound preferably has at least one (meth)acryl fluorenyl group in addition to at least one thermally reactive functional group. In general, a compound having a monofunctional thermally reactive functional group has a low molecular weight and has a problem of volatilization while reacting with heat upon thermal hardening, but has a (meth) acrylonitrile group for inkjet printing. By polymerization at the time of temporary hardening of light, it is possible to obtain good characteristics which are not volatilized when it is hardened by heat.

In the present invention, in particular, as the (C) thermosetting compound, a first thermosetting compound having at least one (meth)acryl fluorenyl group and at least one thermally reactive functional group and at least two heats are preferably used in combination. A second thermosetting compound of a reactive functional group. Thereby, the solder heat resistance can be further improved.

Among the above thermally reactive functional groups, specific examples of the hydroxyl group are 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and pentaerythritol. (meth) acrylate, dipentaerythritol monohydroxypentane (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc., as a commercial item, LIGHT ESTER HO, LIGHT ESTER HOP, LIGHT ESTER HOA (above) It is a trade name of Kyoritsu Chemical Co., Ltd.).

Specific examples of the thermosetting compound having a thermally reactive functional group as a carboxyl group are acrylic acid, methacrylic acid, acrylic acid dimer, 2-methylpropenyloxyethyl succinic acid, methacryloxyethyloxyethyl Hexahydrophthalic acid, monohydroxyethyl phthalate acrylate, etc., as a commercial product, LIGHT ESTER HO-MS, LIGHT ESTER HO-HH (the above is a product name of Kyoeisha Chemical Co., Ltd.) , ARNIX M-5400 (trade name of East Asian Synthetic Chemicals Co., Ltd.), etc.

Specific examples of the thermosetting compound in which the thermoreactive functional group is an isocyanate group are 2-methylpropenyloxyethyl isocyanate (for example, trade name, manufactured by Showa Denko Co., Ltd., MOI).

Specific examples of the thermosetting compound in which the thermally reactive functional group is an amine group are acrylamide, N,N-dimethylaminoethyl acrylate. Ester, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-diethylaminoethyl methacrylate, and the like.

Specific examples of the thermosetting compound in which the thermally reactive functional group is an epoxy group are glycidyl methacrylate, a (meth)acrylonitrile-containing alicyclic epoxy resin, and (meth)acryl oxime. Based on bisphenol A type epoxy resin. Commercial products of the (meth)acrylonitrile-based alicyclic epoxy resin are exemplified by CYCLOMER M100, CYCLOMER A200, and CYCLOMER 2000 (the above are trade names manufactured by DAICEL Co., Ltd.). Commercial products of a bisphenol A type epoxy resin containing a (meth) acrylonitrile group are exemplified by NK OLIGO EA-1010N, EA-1010LC, EA-1010NT (the above are trade names of Shin-Nakamura Chemical Industry Co., Ltd.), and the like. .

Specific examples of the thermosetting compound in which the thermoreactive functional group is an oxetanyl group are (meth)acrylic acid oxetane, etc., and commercially available products include OXE-10 and OXE-30 (Osaka Organic Chemistry). (trade name) (trade name) and so on.

Specific examples of the thermosetting compound whose heat-reactive functional group is a mercapto group are ethyl thioacrylate, ethyl thiomethacrylate, biphenyl thioacrylate, biphenyl thiomethacrylate, and nitrophenyl thioacrylate. , nitrophenyl thiomethacrylate, triphenylmethyl thioacrylate, triphenyl methyl methacrylate, 1,2-bis[(2-mercaptoethyl) thio]-3-mercaptopropane Triacrylate, 2-(mercaptomethyl)-methyl 2-acrylate, 2-[(2-mercaptoethyl)thio]ethyl methacrylate, and the like.

Specific examples of the thermosetting compound having a thermoreactive functional group of a methoxymethyl group are methoxymethyl acrylate and methacrylic acid. Methoxyethyl ester, dimethoxymethyl acrylate, dimethoxymethyl methacrylate, etc., commercially available as NIKALAC MX-302 (acrylic acid modified alkylated melamine, Sanwa Chemical Co., Ltd.) Product name) and so on.

Specific examples of the thermosetting compound having a thermoreactive functional group of a methoxyethyl group are 1-methoxyethyl acrylate, 1-methoxyethyl methacrylate, and 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 thermally reactive functional group is an ethoxyethyl group are 1-ethoxyethyl acrylate, 1-ethoxyethyl methacrylate, and 2-ethoxyethyl acrylate. , 2-ethoxyethyl methacrylate, and the like.

Specific examples of the thermosetting compound in which the thermally reactive functional group is an ethoxymethyl group are N-ethoxymethyl acrylamide, N-ethoxymethyl methacrylamide, ethoxy acrylate. Methyl ester, ethoxymethyl methacrylate, and the like.

A specific example of the thermosetting compound in which the thermally reactive functional group is an oxazoline group is exemplified by 2-methyl-2-{[3-(4,5-dihydro-2-oxazolyl) 2-acrylate. Benzyl hydrazide]amino}ethyl ester, 2-methyl-2-(4,5-dihydro-2-oxazolyl)ethyl 2-acrylate, 3-(4,5- Dihydro-4,4-dimethyl-2-oxazolyl)propyl ester and the like.

Further, as the thermosetting compound having two or more kinds of thermally reactive functional groups, an amine-based resin such as a melamine resin, a benzoquinone resin, a melamine derivative or a benzoquinone derivative, or a blocked isocyanate compound can be used. A conventional thermosetting resin such as a compound, a cyclic carbonate compound, a thermosetting component having a cyclic (thio)ether group, a bismaleimide or a carbodiimide resin. It is particularly preferred to block the isocyanate compound from the viewpoint of excellent preservation stability.

A thermosetting compound having a plurality of cyclic (thio)ether groups in the above molecule, which is any one or two groups of cyclic (thio)ether groups having a plurality of 3, 4 or 5 membered rings in the molecule. a compound, for example, a compound having a plurality of epoxy groups in a molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, having a plurality of sulfur in the molecule; The ether group compound is also an episulfide resin or the like.

Examples of the polyfunctional epoxy compound include ADEKACIZER O-130P, ADEKACIZER O-180A, ADEKACIZER D-32, and ADEKACIZER D-55 manufactured by ADEKA Co., Ltd.; jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation. EPICLON 840, EPICLON 850, EPICLON 1050, EPICLON 2055 manufactured by DIC Corporation, EPITOT YD-011, YD-013, YD-127, YD-128 manufactured by Dongdu Chemical Co., Ltd., DER317, DER331 manufactured by DOW CHEMICAL, DER661, DER664, SUMI EPOXY ESA-011, ESA-014, ELA-115, ELA-128, AER330, AER331, AER661, AER664, etc., manufactured by Sumitomo Chemical Industries Co., Ltd. Commodity name) bisphenol A type epoxy resin; hydroquinone type epoxy resin such as YDC-1312, bisphenol type epoxy resin such as YSLV-80XY, YSLV-120TE and other thioether epoxy resins (all manufactured by Dongdu Chemical Co., Ltd.); jERYL903 manufactured by Mitsubishi Chemical Corporation, EPICLON 152, EPICLON165 manufactured by DIC Corporation, EPITOT YDB-400 and YDB-500 manufactured by Dongdu Chemical Co., Ltd. DER542 manufactured by DOW CHEMICAL Co., Ltd., SUMI EPOXY ESB-400 manufactured by Sumitomo Chemical Industries Co., Ltd., ESB-700, AER711, AER714 manufactured by Asahi Kasei Kogyo Co., Ltd. (both trade names), brominated epoxy resin; Mitsubishi Chemical JER152, jER 154, DEN431, DEN438 manufactured by DOW CHEMICAL, EPICLON N-730, EPICLON N-770, EPICLON N-865, manufactured by Dongdu Chemical Co., Ltd., EPITOT YDCN-701, YDCN- 704, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., SUMI EPOXY ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Industries, Ltd., AER manufactured by Asahi Kasei Kogyo Co., Ltd. Epoxy resin type epoxy resin such as ECN-235, ECN-299 (all are trade names); bisphenol novolac type epoxy resin such as NC-3000 and NC-3100 manufactured by Nippon Kayaku Co., Ltd.; EPICLON 830, jER807 made by Mitsubishi Chemical Corporation, Dongdu Huacheng Ethoxyl YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F-type epoxy resin; Etotech ST-2004, ST-2007, ST-3000 manufactured by Dongdu Chemical Co., Ltd. Named) hydrogenated bisphenol A type epoxy resin; jER604 manufactured by Mitsubishi Chemical Corporation, EPOTOT YH-434 manufactured by Dongdu Chemical Co., Ltd., SUMI EPOXY ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (both trade names) Glyceramine type epoxy resin; B-uret urea type epoxy resin; fat Ring epoxy resin; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN, EPPN-501, EPPN-502 manufactured by DOW CHEMICAL Co., Ltd. (all trade names), trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names), etc., or a mixture of such bisphenols or biphenols; EBPS-200, ADEKA, manufactured by Nippon Kayaku Co., Ltd. Bisphenol S type epoxy resin such as EPX-30 manufactured by DIC Corporation and EXA-1514 (trade name) manufactured by DIC Corporation; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Mitsubishi Tetrahydroxyphenylethane type epoxy resin manufactured by Chemical Company, jERYL-931 (all are trade names); heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Industries Co., Ltd.; Japanese fat Bis-glycidyl phthalate resin such as BRENMER DGT manufactured by the company; tetraglycidyl dimethyl phenol ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN manufactured by Nippon Steel Chemical Co., Ltd. -360, naphthalene-based epoxy resin such as HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation; HP-7200 and HP-72 manufactured by DIC Corporation Epoxy resin having a dicyclopentadienyl structure such as 00H; glycidyl methacrylate copolymerized epoxy resin of CP-50S, CP-50M, etc. manufactured by Nippon Oil Co., Ltd.; and further cyclohexylmaleimide a copolymerized epoxy resin with glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative, a CTBN-modified epoxy resin (for example, YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd.), But not limited to these. These epoxy resins may be used singly or in combination of two or more. Among these, a novolac type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, a biphenol novolac is particularly preferable. Varnish type epoxy resin, naphthalene type epoxy resin or a mixture of these.

As the polyfunctional oxetane compound, for example, 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-oxetanyl) Oxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-oxetanyl)methyl acrylate, methacrylic acid (3- Methyl-3-oxetanyl)methyl ester, (3-ethyl-3-oxetanyl)methyl methacrylate or a polyfunctional oxygen heterocycle such as an oligomer or copolymer thereof Butanes, further examples are oxetane and novolak resins, poly(p-hydroxystyrene), cardo bisphenols, calixarenes, resorcinol calixarenes (calix resorcinarenes) An etherified product of a resin having a hydroxyl group such as a sesquioxane or the like. Further, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate or the like is also exemplified.

The compound having a plurality of cyclic thioether groups in the molecule is exemplified by bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Further, an episulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by the same synthesis method may be used.

Examples of the amine-based resin such as a melamine derivative or a benzoquinone derivative include a methylol melamine compound, a hydroxymethyl benzoquinone compound, a methylol glycol urea compound, and a methylol urea compound. Further, an alkoxymethylated melamine compound, an alkoxymethylated benzoquinone compound, an alkoxymethylated glycol urea compound, and an alkylmethylated urea compound can be The methylol melamine compound, the hydroxymethyl benzoquinone compound, the methylol glycol urea compound, and the methylol group of the methylol urea compound are converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and may, for example, be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group or a butoxymethyl group. Particularly preferred is a melamine derivative having a formaldehyde concentration of 0.2% by mass or less which is excellent for the human body or the environment.

As such commercial products, for example, CYMEL 300, CYMEL 301, CYMEL 303, CYMEL 370, CYMEL 325, CYMEL 327, CYMEL 701, CYMEL 266, CYMEL 267, CYMEL 238, CYMEL 1141, CYMEL 272, CYMEL 202, CYMEL are exemplified. 1156, CYMEL 1158, CYMEL 1123, CYMEL 1170, CYMEL 1174, CYMEL UFR65, CYMEL 300 (both manufactured by Mitsui CYANAMIDE), NIKALAC Mx-750, NIKALAC Mx-032, NIKALAC Mx-270, NIKALAC Mx-280, NIKALAC Mx -290, NIKALAC Mx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALAC Mx-31, NIKALAC Ms-11, NIKALAC Mw-30, NIKALAC Mw-30HM, NIKALAC Mw-390, NIKALAC Mw-100LM, NIKALAC Mw -750LM (all manufactured by Sanwa Chemical Co., Ltd.) and the like.

The isocyanate compound and the blocked isocyanate compound are compounds having a plurality of isocyanate groups or blocked isocyanate groups in one molecule. The compound having a plurality of isocyanate groups or blocked isocyanate groups in one molecule is exemplified by a polyisocyanate compound or a blocked isocyanate compound. Further, the blocked isocyanate-based isocyanate group is The terminal blocking agent is protected from the group which is temporarily inactivated, and when it is heated to a specific temperature, its blocking group dissociates to form an isocyanate group. By adding the above-mentioned isocyanate compound or blocked isocyanate compound, it was confirmed that the hardenability and the toughness of the obtained cured product can be improved.

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

Specific examples of the aromatic polyisocyanate are, for example, 4,4'-diphenylmethane diisocyanate, 2,4-xylenyl diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, O-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene dimer, and the like.

Specific examples of the aliphatic polyisocyanate are tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylene double (ring). Hexyl isocyanate) and isophorone diisocyanate.

A specific example of the alicyclic polyisocyanate is biscycloheptane triisocyanate. Further, an adduct, a uret, an isocyanurate or the like of the isocyanate compound exemplified above is exemplified.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. The isocyanate compound which can be reacted with a blocking agent is exemplified by, for example, the above polyisocyanate compound.

Examples of the isocyanate blocking agent include phenolic terminal blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valeroinamide, and γ-butene Amine, and β-propionamide, etc. a terminal agent; an active methylene-based blocking agent such as ethyl acetate and ethyl acetonylacetate; methanol, ethanol, propanol, butanol, pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Alcohol seals such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate Terminal agent; anthraquinone blocking agent such as formaldehyde hydrazine, acetald oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine, cyclohexanone oxime, etc.; butyl mercaptan, hexyl mercaptan, third a thiol-based blocking agent such as butyl thiol, thiophenol, methyl thiophenol or ethyl thiophenol; a guanamine-based blocking agent such as decylamine or benzylamine; yttrium succinate and horse An imide-based blocking agent such as imine or the like; an amine-based blocking agent such as xylidine, benzylamine, butylamine or dibutylamine; an imidazole-based seal such as imidazole or 2-ethylimidazole Terminal agent; imine-based terminal blocking agent such as methyleneimine and propylimine.

Blocked isocyanate compounds are also commercially available, such as SUMIDUR BL-3175, BL-4165, BL-1100, BL-1265, DESMODUR TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, DESMOTHERM 2170, DESMOTHERM 2265 (both manufactured by Sumitomo Bayer Carbamate), CORONATE 2512, CORONATE 2513, CORONATE 2520 (all manufactured by Japan Polyurethane Industrial Co., Ltd.), B-830, B-815, B-846, B-870, B-874, and B-882 (both manufactured by Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, and E402-B80T (all manufactured by Asahi Kasei Chemicals Co., Ltd.). Further, SUMIDUR BL-3175 or BL-4265 can also be used as a terminal blocking agent for methyl ethyl hydrazine. The compound having a complex isocyanate group or a blocked isocyanate group in one molecule may be used singly or in combination. Two or more types are used.

(C) The compounding ratio of the thermosetting compound is preferably from 10 to 70 parts by mass, more preferably from 20 to 60 parts by mass, per 100 parts by mass of the curable composition of the present invention. When the amount is 10 parts by mass or more, sufficient coating film toughness and heat resistance are obtained. On the other hand, when it is 70 parts by weight or less, it is possible to suppress a decrease in storage stability. (C) The thermosetting compound may be used alone or in combination of two or more.

[(D) Epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group]

The epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group is exemplified by a bisphenol A type epoxy (meth) acrylate resin, a bisphenol F type epoxy (meth) acrylate resin. , bisphenol E type epoxy (meth) acrylate resin, cresol novolak type epoxy (meth) acrylate resin, phenol novolak type epoxy (meth) acrylate resin, aliphatic epoxy (A Base) acrylate and the like.

Examples of the bisphenol A type epoxy (meth) acrylate resin are EBECRYL 600, EBECRYL 605, EBECRYL 648, EBECRYL 3700, EBECRYL 3703 (the above are trade names of DAICEL ALLNEX), EPOXY ESTER EX-0205, EPOXY ESTER. 3000A, EPOXY ESTER 3002A (N) (above is the trade name of Kyori Chemical Co., Ltd.), 8026, 8101, 8125, 8197, 8250 LMH, 8260, 8355, 8360BR, 8327, 8351 (above Japanese U-PICA company) Product name), HITAROID 7851 (The above-mentioned product name of Hitachi Chemical Co., Ltd.), BISCOTE #540 (trade name of Osaka Organic Chemical Industry Co., Ltd.), CN104, CN104A80, CN104B80, CN120, CN120A60, CN120A75, CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN120E50 , CN120M50, CN151 (trade name of SATOMER Co., Ltd.), Miramer PE210 (trade name of Toyo Chemical Co., Ltd.), NK OLIGO EA-1010N, EA-1010LC, EA-1010NT, EA-1020, EA-1020LC3, EMA -1020 (the product name of the above-mentioned New Nakamura Chemical Industry Co., Ltd.).

Examples of the bisphenol F-type epoxy (meth) acrylate resin are 8475 and 8476 (trade names manufactured by U-PICA Co., Ltd., Japan).

Examples of the cresol novolac type epoxy (meth) acrylate resin are NK OLIGO EA-7120/PGMAC, EA-7140/PGMAC, EA-7420/PGMAC (trade name manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like.

Examples of the phenol novolac type epoxy (meth) acrylate resin are 8400, 8411 LH (trade name manufactured by U-PICA Co., Ltd., Japan), HITAROID 7663 (trade name manufactured by Hitachi Chemical Co., Ltd.), and NK OLIGO EA-6320. /PGMAC, EA-6340/PGMAC (trade name of New Nakamura Chemical Industry Co., Ltd.), etc.

Examples of the aliphatic epoxy (meth) acrylate are EBECRYL 3500, EBECRYL 3608, and EBECRYL 3702 (above DAICEL ALLNEX company name), Miramer PE230 (trade name by Toyo Chemical Co., Ltd.), etc.

Among the above epoxy (meth) acrylate resins, bisphenol A type epoxy (meth) acrylate resin and bisphenol F type epoxy (meth) acrylate resin which are relatively low in viscosity and excellent in heat resistance are preferable. A bisphenol type epoxy (meth) acrylate resin such as a bisphenol E type epoxy (meth) acrylate resin.

Moreover, the viscosity of the epoxy (meth) acrylate resin at 40 ° C is preferably from 100 to 40,000 mPa. The range of s. The blending ratio of the epoxy (meth) acrylate resin is preferably from 5 to 50 parts by mass, more preferably from 10 to 35 parts by mass, per 100 parts by mass of the hard composition of the present invention. When the 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 the amount is 50 parts by mass or less, good coating properties are obtained which are improved in compatibility and uniformly dispersed. The epoxy (meth) acrylate resin may be used singly or in combination of two or more.

[(E) 2-functional (meth) acrylate compound]

The curable composition of the present invention may further contain (E) a bifunctional (meth) acrylate compound. The (E) bifunctional (meth) acrylate compound is used as a reactive diluent, and is preferable because the balance between the dilution effect and the heat resistance is good. By formulating the (E) bifunctional (meth) acrylate compound, the viscosity of the curable composition can be reduced. A specific example of the bifunctional (meth) acrylate compound is 1,4-butanediol dipropylene. Diacrylate, ethylene glycol diacrylic acid of diol, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-nonanediol diacrylate, etc. Ester, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylic acid Ester, neopentyl glycol diacrylate, diol diacrylate obtained by adding at least one of neopentyl glycol to ethylene oxide and propylene oxide, caprolactone modified hydroxypivalic acid neopentyl glycol Diacrylate of diacrylate or the like, bisphenol A EO adduct diacrylate, bisphenol A PO adduct diacrylate, bisphenol A diglycidyl ether acrylic acid adduct, tricyclodecane Dimethacrylate diacrylate, di(2-hydroxyethyl)isocyanurate bisphenol A addition of at least one of ethylene oxide and propylene oxide, diacrylate, hydrogenated dicyclopentane Diacrylate, isocyanuric acid having a cyclic structure such as diene diacrylate or cyclohexyl diacrylate Ethylene oxide-modified diacrylate isobutyl, etc. The cyanurate diacrylate and the like.

As a commercially available product, tetraacrylate 1,6HX-A, 1,9ND-A, 3EG-A, 4EG-A (trade name of Kyoei Chemical Co., Ltd.), HDDA, 1,9-NDA, DPGDA are exemplified. TPGDA (trade name by DAICEL ALLNEX), BISCOTE #195, #230, #230D, #260, #310HP, #335HP, #700HV, #540 (trade name by Osaka Organic Chemical Industry Co., Ltd.), ARONIX M -208, M-211B, M-215, M-220, M-225, M-240, M-270 (trade name manufactured by Toagosei Co., Ltd.), and the like.

Among the bifunctional (meth) acrylates, based on viscosity and phase From the viewpoint of solubility, a diacrylate having a diol having an alkyl chain is preferred. Among them, a diacrylate having a diol having an alkylene chain having 4 to 12 carbon atoms is more preferable. As an example, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, etc. are illustrated.

Further, the blending ratio of the (E) bifunctional (meth) acrylate compound is preferably from 10 to 80 parts by mass, more preferably from 30 to 60 parts by mass, per 100 parts by mass of the curable composition of the present invention. The scope. When the amount of the (E) bifunctional (meth) acrylate compound is 10 parts by mass or more, good coating properties are obtained which are improved in compatibility and uniform dispersion, and when the amount is 80 parts by mass or less, an effect of improving heat resistance is obtained. (E) The bifunctional (meth) acrylate compound may be used alone or in combination of two or more.

Further, in the curable composition of the present invention, a reactive diluent other than the (E) bifunctional (meth) acrylate compound may be blended. By formulating a reactive diluent, the viscosity of the curable composition can be lowered. As other reactive diluents, photoreactive diluents, heat reactive diluents and the like are exemplified. Among these, a photoreactive diluent is preferred.

As the photoreactive diluent, for example, (meth) acrylates, vinyl ethers, ethylene derivatives, styrene, chloromethyl styrene, α-methyl styrene, maleic anhydride, dicyclopentadiene , N-vinylpyrrolidone, N-vinylformamide, xylene dioxetane, oxetane, 3-ethyl-3-(phenoxymethyl)oxyheterocycle Butane, cresol diglycidyl ether, etc. having an unsaturated double bond or an oxetanyl group or an epoxy group Compound.

Among these, (meth) acrylates are preferable, and as the (meth) acrylate, the above (E) bifunctional (meth) acrylate compound, for example, a monofunctional (meth) acrylate may be used. A compound, a trifunctional (meth) acrylate compound, or the like.

As the monofunctional (meth) acrylate compound, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (methyl) (Meth) acrylates such as lauryl acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Or acryloylmorpholine and the like. Specific examples of the trifunctional (meth) acrylate compound are trimethylolpropane triacrylate, pentaerythritol triacrylate, trimethylolpropane PO modified triacrylate, and trimethylolpropane EO modified three. A trifunctional acrylate such as an acrylate or a trifunctional polyester acrylate.

The blending ratio of the other reactive diluents is preferably from 1 to 70 parts by mass, more preferably from 5 to 60 parts by mass, per 100 parts by mass of the curable composition of the present invention. When the amount of the other reactive diluent is 1 part by mass or more, good coating properties are obtained which are improved in compatibility and uniform dispersion, and when the amount is 70 parts by mass or less, an effect of improving heat resistance is obtained. The other reactive diluents may be used alone or in combination of two or more.

Further, in the curable composition of the present invention, the blending amount of the monofunctional reactive diluent is preferably as small as possible, specifically, the hardening of the present invention. In 100 parts by mass of the sexual composition, it is preferably 10 parts by mass or less. When the amount of the monofunctional reactive diluent is small, the crosslinking density can be increased, and the characteristics such as solder heat resistance can be further improved.

In the curable composition of the present invention, a thermosetting catalyst can be further adjusted. The thermosetting catalyst is used to further improve the thermosetting property of the (C) thermosetting compound, and an amine compound such as dicyandiamide or an aromatic amine, an imidazole, a phosphorus compound, an acid anhydride, or a bicyclic hydrazine can be used. Compounds, etc. Specifically, imidazole, 1-benzyl-2-phenylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4- Imidazoles such as phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodicimamine, Benzyl dimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N, An amine compound such as N-dimethylbenzylamine or a phosphorus compound such as triphenylphosphine. More specifically, as the imidazole compound, for example, 1B2PZ, 2E4MZ, 2MZ-A, 2MZ-OK, 2PHZ, 2P4MHZ (manufactured by Shikoku Chemical Industries Co., Ltd.); and a blocked isocyanate compound as dimethylamine are exemplified as U. -CAT3503N, -3502T (made by SAN APRO Co., Ltd.); as a bicyclic oxime compound and its salt, DBU, DBN, U-CAT SA102, U-CAT5002 (made by SAN APRO company), etc. are mentioned. These may be used alone or in combination of two or more.

The content of the thermosetting catalyst is sufficient, and is, for example, preferably 0.1 to 10 parts by mass based on 100 parts by mass of the (C) thermosetting compound.

In the curable composition of the present invention, in addition to the above components, a surface tension adjusting agent, a surfactant, a matting agent, a polyester resin for adjusting the physical properties of the film, and a polyurethane resin may be blended as needed. Conventional colorants such as vinyl resin, acrylic resin, rubber resin, wax, red, blue, green, yellow, white, black, etc., such as phthalocyanine blue, phthalocyanine green, iodine green, bisazo At least one of antifoaming agents and leveling agents such as yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and the like, such as an imidazole, a thiazole, or a triazole. A conventionally used additive such as a tackifier for a decane coupling agent or the like.

The curable composition of the present invention having the above respective components is used in a printing method of an inkjet method. Based on this aspect, the curable composition of the present invention has a viscosity of 50 mPa at 50 ° C. Below s, especially good is 10~30mPa. s. Thereby, unnecessary loading is not imposed on the ink jet printer, and smooth printing can be performed. Moreover, the viscosity of the curable composition of the present invention at room temperature is suitably 150 mPa. In the following, the printing by the inkjet printing method can be performed favorably. Here, in the present invention, the viscosity refers to the viscosity measured at room temperature (25 ° C) or 50 ° C in accordance with JIS K2283.

Further, the curable composition of the present invention can be printed on a flexible circuit board by a roll-to-roll method. In this case, the resist pattern can be formed at a high speed by mounting a light source for light irradiation to be described later after passing through the ink jet printer.

The light irradiation is performed by irradiation of ultraviolet rays or active energy rays, but is preferably ultraviolet light. As the light source for light irradiation, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a metal halide lamp, and an LED lamp having a wavelength in an ultraviolet region of 365, 385, 395, and 405 nm are preferable. Further, an electron beam, an α -ray, a β -ray, a γ -ray, an X-ray, a neutral beam or the like can also be used. Further, it is hardened by heating after light irradiation as needed. Here, the heating temperature is, for example, 80 to 200 °C. By setting it as this heating temperature range, it can fully harden. The heating time is, for example, 10 to 100 minutes.

The curable composition of the present invention can obtain a hardened coating film having a high hardness by applying at least either or both of the above-described light irradiation and heating to the coating film obtained by the ink jet printing. The curable composition of the present invention can form a pattern-hardened coating film which is excellent in adhesion to a substrate and excellent in solder heat resistance, gold plating resistance, pencil hardness, chemical resistance, and flexibility.

The curable composition of the present invention can be preferably used as a permanent insulating film such as a solder resist for a printed circuit board. Further, the printed circuit board of the present invention has a feature of having a cured coating film formed using the above-described curable composition of the present invention on a substrate.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples and comparative examples, but the invention is not limited by the examples and the comparative examples.

According to the formulation described in the following Table 1, the materials described in the examples and the comparative examples were prepared and mixed in advance by a stirrer to prepare a curable composition. Further, the value of the blending amount in the table is a mass fraction of the solid component unless otherwise specified.

*1-5) IRGACURE 819, manufactured by BASF, Japan, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (bis-decylphosphine oxide)

*1-6) BI7982, a trifunctional blocked isocyanate manufactured by Baxenden Chemical Co., Ltd.

*1-7) 4HBA, manufactured by Nippon Kasei Co., Ltd., 4-hydroxybutyl acrylate

*1-8) EA-1010N, manufactured by Shin-Nakamura Chemical Co., Ltd., containing (meth)acrylonitrile-based bisphenol A epoxy resin (monofunctional), viscosity at 40 ° C 10,000 ~ 30,000 mPa. s

*1-9) A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., 1,9-nonanediol diacrylate (2-functional acrylate monomer)

*1-10)FASTOGEN BLUE 5380, manufactured by DIC, phthalocyanine blue (pigment)

*1-11) Cromophtal yellow AGR, manufactured by BASF, Japan, cromophtal yellow (pigment)

The curable composition of each of the obtained examples and comparative examples was evaluated in accordance with the following. The results are shown in Table 2 below.

(1) Viscosity at 50 ° C

The viscosity of the curable composition obtained in each of the examples and the comparative examples at 50 ° C and 100 rpm was measured by a laminar type viscometer (TVH-33H manufactured by Toki Sangyo Co., Ltd.). The results were evaluated based on the following criteria.

○: More than 10mPa. s and 50mPa. s below.

△: more than 50mPa. s and 200mPa. s below.

×: More than 200mPa. s.

(2) Adhesion test

The sclerosing compositions obtained in Examples 1-1 to 1-6 and Comparative Examples were applied to a copper-clad laminate using a 30 μm applicator (manufactured by ERICHSEN Co., Ltd.), and a high-pressure mercury lamp (HMW-713 manufactured by ORC Co., Ltd.). Hardening was performed at 150 mJ/cm ² . In the example 1-7, the curable composition was subjected to inkjet coating on a copper-clad laminate using a MATERIAL PRINTER DMP-2831 manufactured by FUJIFILM GLOBAL GRAPHIC SYSTEM, and an LED lamp (ANUJ6164 manufactured by PANASONIC) was 150 mJ/cm ^{2 .} Harden. Subsequently, heat treatment was carried out for 60 minutes in a hot air circulating drying oven at 150 °C. A cross-cut tape peeling test was performed on the produced samples. As a result, it is calculated how many of the remaining number of the checkerboards are left in 100, and evaluation is performed based on the following criteria.

◎: 100/100.

○: 80~99/100

△: 60~79/100.

×: 59 or less / 100.

(3) Pencil hardness (surface hardness)

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

(4) Solder heat resistance

The rosin-based flux was applied onto the cured coating film of each of the examples and the comparative examples obtained under the above-mentioned substrate production conditions, and immersed in a solder bath at 260 ° C for 10 seconds for 3 times, and then subjected to cross-cut tape peeling. test. As a result, it is calculated how many of the remaining number of the checkerboards are left in 100, and evaluation is performed based on the following criteria.

◎: 100/100.

○: 80~99/100

△: 60~79/100.

×: 59 or less / 100.

(5) Gold plating resistance

The hardened coating films of the respective examples and comparative examples obtained under the conditions for the substrate production of the above (2) were plated with nickel 0.5 μm and gold 0.03 μm using a commercially available electroless nickel plating bath and an electroless gold plating bath. Apply and perform a cross-cut tape peeling test. As a result, it is calculated how many of the remaining number of the checkerboards are left in 100, and evaluation is performed based on the following criteria.

◎: 100/100.

○: 80~99/100

△: 60~79/100.

×: 59 or less / 100.

As shown in the above table, the curable composition of each of the examples of the urethane (meth) acrylate resin having a specific functional number and the photopolymerization initiator was confirmed to have solder heat resistance and gold plating resistance. In addition, it also has good adhesion on the substrate, has high hardness after hardening, and has a low viscosity suitable for inkjet printing.

In Examples 1-1 to 1-4, a polyfunctional and low-viscosity aliphatic 6-functional urethane acrylate oligomer was used as the urethane (meth) acrylate resin, and it was found that a low viscosity was obtained. A hardening composition of high hardness. Further, regarding Examples 1-5 to 1-7 in which a polyfunctional and low-viscosity aromatic 6-functional urethane acrylate oligomer is also used as the urethane (meth) acrylate resin, A hardening composition having low viscosity and high hardness is obtained.

On the other hand, in Comparative Example 1-1 containing no urethane (meth) acrylate resin, solder heat resistance and gold plating resistance were inferior. Further, in Comparative Examples 1-2 to 1-4 which did not contain a thermosetting compound, solder heat resistance and gold plating resistance were further lowered, and adhesion was deteriorated, and Comparative Example 1-4 containing no bifunctional acrylate monomer was further contained. , becoming highly viscous and not suitable for spraying Ink printer.

According to the formulation described in the following Table 3, the materials described in the examples and the comparative examples were prepared and mixed in advance by a stirrer to prepare a curable composition. Further, the value of the blending amount in the table is a mass fraction of the solid component unless otherwise specified.

Viscosity is 1,000~3,000mPa. s

*2-3) DM776, an aromatic 6-functional urethane acrylate oligomer manufactured by DOUBLE BOND CHEMICAL Co., Ltd., viscosity at 25 ° C 4,000 ~ 6,000 mPa. s

*2-4) DAROCURE 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-trimethylbenzylidene)-phenylphosphine oxide (bis-decylphosphine oxide)

*2-6) A-NOD-N, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., 1,9-nonanediol diacrylate (2-functional acrylate monomer)

*2-7) EA-1010N, manufactured by Shin-Nakamura Chemical Co., Ltd., containing (meth)acrylonitrile-based bisphenol A epoxy resin (monofunctional), viscosity at 40 ° C 10,000 ~ 30,000 mPa. S

*2-8) 3002A(N), PO-modified bisphenol A epoxy acrylate (bisphenol A PO2mol adduct, diglycidyl ether acrylic acid adduct)

*2-9) 4HBA, manufactured by Nippon Kasei Co., Ltd., 4-hydroxybutyl acrylate

*2-10) BI7982, manufactured by Baxenden, a trifunctional blocked isocyanate

*2-11)FASTOGEN BLUE 5380, manufactured by DIC, phthalocyanine blue (pigment)

*2-12) cromophtal yellow AGR, manufactured by BASF, Japan, cromophtal yellow (pigment)

The curable composition of each of the obtained examples and comparative examples was evaluated in accordance with the following. The results are shown in Table 4 below.

(1) Viscosity at 50 ° C

The viscosity of the curable composition obtained in each of the examples and the comparative examples at 50 ° C and 100 rpm was measured by a laminar type viscometer (TVH-33H manufactured by Toki Sangyo Co., Ltd.). The results were evaluated based on the following criteria.

○: More than 10mPa. s and 50mPa. s below.

△: more than 50mPa. s and 200mPa. s below.

×: More than 200mPa. s.

(2) Adhesion test

The sclerosing compositions obtained in Examples 2-1 to 2-7 and Comparative Examples were applied to a copper-clad laminate using a 30 μm applicator (manufactured by ERICHSEN Co., Ltd.), and a high-pressure mercury lamp (HMW-713 manufactured by ORC Co., Ltd.). Hardening was performed at 150 mJ/cm ² . In the example 2-8, the curable composition was subjected to inkjet coating on a copper-clad laminate using a MATERIAL PRINTER DMP-2831 manufactured by FUJIFILM GLOBAL GRAPHIC SYSTEM, and an LED lamp (ANUJ6164 manufactured by PANASONIC) was 150 mJ/cm ^{2 .} Harden. Subsequently, heat treatment was carried out for 60 minutes in a hot air circulating drying oven at 150 °C. A cross-cut tape peeling test was performed on the produced samples. As a result, it is calculated how many of the remaining number of the checkerboards are left in 100, and evaluation is performed based on the following criteria.

◎: 100/100.

○: 80~99/100

△: 60~79/100.

×: 59 or less / 100.

(3) Pencil hardness (surface hardness)

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

(4) Solder heat resistance

The rosin-based flux was applied onto the cured coating film of each of the examples and the comparative examples obtained under the above-mentioned substrate production conditions, and immersed in a solder bath at 260 ° C for 10 seconds for 3 times, and then subjected to cross-cut tape peeling. test. As a result, it is calculated how many of the remaining number of the checkerboards are left in 100, and evaluation is performed based on the following criteria.

◎: 100/100.

○: 80~99/100

△: 60~79/100.

×: 59 or less / 100.

(5) Gold plating resistance

The hardened coating films of the respective examples and comparative examples obtained under the conditions for the substrate production of the above (2) were plated with nickel 0.5 μm and gold 0.03 μm using a commercially available electroless nickel plating bath and an electroless gold plating bath. Apply, implement a cross Cutting tape peeling test. As a result, it is calculated how many of the remaining number of the checkerboards are left in 100, and evaluation is performed based on the following criteria.

◎: 100/100.

○: 80~99/100

△: 60~79/100.

×: 59 or less / 100.

As shown in the above table, the curable composition of each of the examples of the urethane (meth) acrylate resin having a specific functional number and the photopolymerization initiator was confirmed to have solder heat resistance and gold plating resistance. In addition, it also has good adhesion on the substrate, has high hardness after hardening, and has a low viscosity suitable for inkjet printing.

Examples 2-1 to 2-4 use a polyfunctional and low-viscosity aliphatic 6-functional urethane acrylate oligomer as a urethane (meth) acrylate resin to obtain low viscosity and high When the amount of the urethane (meth) acrylate resin as in Example 2-5 was too large, the viscosity was high. Again, about the same use A polyfunctional and low-viscosity aromatic 6-functional urethane (meth) acrylate oligomer is obtained as a urethane (meth) acrylate resin in Examples 2-6 to 2-8. A hardening composition of viscosity and high hardness.

On the other hand, in Comparative Example 2-1 containing no urethane (meth) acrylate resin or Comparative Example 2-2 containing no epoxy (meth) acrylate resin, solder heat resistance and gold plating resistance became Poor results. Further, Comparative Example 2-3 which does not contain a bifunctional acrylate monomer has a high viscosity and is not suitable for inkjet printers.

Claims (11)

A curable composition for inkjet, which comprises (A) a urethane (meth) acrylate resin having a functional group of at least 5 functional groups and not more than (B) a photopolymerization initiator. 1. The curable composition for inkjet according to claim 1, wherein the (A) urethane (meth) acrylate resin has a viscosity at 25 ° C of 1,000 to 20,000 mPa. s. The curable composition for inkjet according to claim 1, which further comprises (C) a thermosetting compound having at least one thermally reactive functional group (removing an epoxy having at least one (meth) acrylonitrile group (A) Base) acrylate resin). The curable composition for inkjet according to claim 3, wherein the (C) thermosetting compound (excluding an epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group) has at least a first thermosetting compound having one (meth)acrylinyl group and at least one thermally reactive functional group, and a second thermosetting compound having at least two thermally reactive functional groups. The curable composition for inkjet according to claim 1, which further comprises (D) an epoxy (meth) acrylate resin having at least one (meth) acrylonitrile group. The curable composition for inkjet according to claim 5, wherein the (D) epoxy (meth) acrylate resin is a bisphenol epoxy (meth) acrylate resin. The curable composition for inkjet according to claim 1, which further comprises (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, which has a viscosity of 50 mPa at 50 ° C. s below. A hardened coating film characterized in that the curable composition for inkjet according to claim 1 is cured. A printed circuit board characterized by having a hard coat film as claimed in claim 10 on a substrate.