JP2019178287A - Curable composition for inkjet printing, cured product of the same and electronic component having the cured product - Google Patents

Abstract

To provide a curable composition for inkjet printing, of which a coating film obtained therefrom shows improved heat resistance compared to the prior arts.SOLUTION: The curable composition for inkjet printing comprises (A) a (meth)acrylate monomer having a cyclic skeleton and an alkylene oxide modification number of 1 or more and 6 or less, (B1) a difunctional (meth)acrylate monomer having two or more alkylene glycol structures and no cyclic skeletons, (B2) a difunctional (meth)acrylate monomer having a monoalkylene glycol structure and no cyclic skeletons, and (C) a photopolymerization initiator. A coating film obtained from the composition has no cracks even after subjected to a thermal history assuming a plurality of times of soldering, shows excellent adhesiveness to a conductor and maintains sufficient hardness.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, and more particularly to a curable composition applicable to printing by an inkjet method. The present invention also relates to a cured product of the curable composition and an electronic component having the cured product.

  Conventionally known curable compositions used for thermosetting, ultraviolet curable, and alkali development type solder resists contain high molecular weight polymers in the composition in accordance with requirements such as heat resistance. . However, when the viscosity of the curable composition is lowered for application to ink jet printing, these high molecular weight polymers have high viscosity and cannot be used.

  Therefore, in recent years, the composition of a curable composition used for a solder resist for inkjet printing has been designed around a low-viscosity monomer. For example, Patent Document 1 discloses a curable composition that can be used for printing by an inkjet method.

  Since the curable composition of Patent Document 1 has a monomer-based composition, it has a low viscosity and can be applied as an ink for an ink jet printer, and can print a pattern directly on a substrate for a printed wiring board. It is possible to save the labor of forming a resist pattern by exposure and development as in the photographic development method, and to reduce the amount of materials such as a photosensitive resin material, a developing solution, and a cleaning solvent used for forming the resist pattern. it can.

  Similarly, it is not necessary to perform plate making as in the case of forming a resist pattern by a screen printing method, so that labor can be saved and the amount of materials such as emulsion can be reduced.

  Patent Document 2 is a photocurable inkjet ink, as in Patent Document 1, and is a radical polymerizable urethane (meth) acrylate oligomer, at least one radical polymerizable monomer, a photo radical polymerization initiator, and glycol ethers. A photocurable ink-jet ink comprising a non-reactive diluent is disclosed.

  Patent Document 3 discloses an active energy ray-curable composition for optical components that can be used to form a solder resist for flexible printed wiring, although it is not a resin composition for inkjet. Specifically, the active energy ray-curable composition for optical parts includes a urethane polyfunctional (meth) acrylate oligomer (A), a bifunctional polyoxyalkylene polyol (meth) acrylate (B) not containing an aromatic ring, 3 to 6 functional (meth) acrylate (C), monofunctional (meth) acrylate (D) not containing urethane groups based on the total amount of components (A) to (D), and light Contains a polymerization initiator (E).

International Publication No. 2013/146706 Japanese Patent Laid-Open No. 2006-124907 JP 2017-083668 A

  However, since the curable composition used in the conventional ink jet printing method, such as the curable composition of Patent Document 1, has a monomer-based structure, it has a low viscosity, a low molecular weight, and is compared with a composition mainly using a polymer. Thus, the cured product after curing is presumed to have a low molecular weight.

  For this reason, it is difficult to obtain the same heat resistance as when using a polymer when used for the production of a solder resist for ink jet printing, and the inventor may experience problems such as cracks in the coating film due to thermal history such as reflow. It was found by their examination.

  Specifically, when a component is mounted on a double-sided board with wiring printed on both sides of the board or a multilayer board in which the board is laminated, the solder resist from the conductor in the land, which is the mounting site of the part, is repeatedly heated. It has been found that defects such as peeling of the coating or cracks in the solder resist itself may occur.

  According to the photocurable inkjet ink of Patent Document 2, although the storage stability of the photocurable inkjet ink is improved by the non-reactive diluent which is a glycol ether, the heat resistance of the film formed from the ink is improved. There is no mention of measures for this.

  Since the active energy ray-curable composition for optical parts of Patent Document 3 is a composition mainly composed of an acrylate monomer as in Patent Document 1, it is considered that the obtained cured product is also vulnerable to repeated heating. Is a solder resist for flexible printed wiring having a relatively small thermal history. Note that the active energy ray-curable composition for optical components of Patent Document 3 is not an ink jet printing composition.

  This invention is made | formed in view of the said subject, The objective used the curable composition for inkjet printing in which the heat resistance of the obtained film improved more than before, its hardened | cured material, and hardened | cured material. To provide electronic components.

  In order to increase the heat resistance of the cured film of the acrylate monomer-based curable composition used in the ink jet printing method, the compounded acrylate monomer was examined, and among the acrylate monomers for dilution added to reduce the viscosity. Although it tends to cause cracks in the film after repeated heating, it has excellent other mechanical properties (adhesion with conductor, film hardness, chemical resistance, hereinafter also referred to as solder heat resistance), and cracks after heating It has been clarified by the inventors that there are some materials that suppress solder generation but have poor solder heat resistance.

The present invention has been made for the purpose of improving the heat resistance of the coating film, including the suppression of the occurrence of cracks after heating, based on the above examination results. That is, the above object of the present invention is to provide a curable composition for inkjet printing.
(A) a (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 to 6;
(B1) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures;
(B2) a bifunctional (meth) acrylate monomer that does not have a cyclic skeleton and has a monoalkylene glycol structure;
And (C) a photopolymerization initiator.

  In the curable composition for inkjet printing of the present invention, the amount of (meth) acrylate monomer having (A) a cyclic skeleton per 100 parts by mass of the curable composition and having an alkylene oxide modification number of 1 or more and 6 or less. Is preferably 5 parts by mass or more and 40 parts by mass or less.

  Furthermore, (B1) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures and (B2) a bifunctional (meth) acrylate having no monocyclic glycol structure and having no cyclic skeleton. The mass ratio ((A) / (B1) + (B2)) of the (meth) acrylate monomer having (A) a cyclic skeleton with respect to the total amount of rate monomers and having an alkylene oxide modification number of 1 or more and 6 or less is 0. It is preferably 10 or more and 0.70 or less.

  Moreover, (B2) a bifunctional (meth) having no cyclic skeleton and having a bifunctional (meth) acrylate monomer having a monoalkylene glycol structure (B1) having no cyclic skeleton and having two or more alkylene glycol structures The mass ratio of acrylate monomers ((B1) / (B2)) is preferably 1.0 or more and 3.0 or less.

  The above-mentioned object of the present invention is also achieved by a cured product of the curable composition of the present invention and an electronic component having the cured product.

  According to the present invention, the film (cured product) formed from the curable composition for ink jet printing is free from cracks even after repeated heating assuming reflow soldering, and after soldering or plating. In this case, sufficient adhesion to the substrate (solder heat resistance, plating resistance) and film hardness are maintained, and it has good mechanical characteristics expected as a solder resist.

FIG. 1 is a graph showing conditions for reflow treatment of a curable composition according to an example of the present invention to a cured product (test substrate).

<Curable composition for inkjet printing>
The curable composition for inkjet printing of the present invention (hereinafter sometimes abbreviated as “curable composition”)
(A) a (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 to 6;
(B1) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures;
(B2) a bifunctional (meth) acrylate monomer that does not have a cyclic skeleton and has a monoalkylene glycol structure;
(C) a photopolymerization initiator.

[(A) (Meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 to 6]
(A) A (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 or more and 6 or less has a relatively high viscosity, but is a crack after repeated reflow of a coating obtained by being added It is a monomer that improves resistance and solder heat resistance.

  The cyclic skeleton includes a cyclic carbon skeleton in which the ring structure is formed of only carbon, and a heterocyclic skeleton containing atoms other than carbon atoms such as oxygen atoms, nitrogen atoms, and sulfur atoms in the ring structure. Furthermore, the ring structure may be an aromatic ring or a saturated or unsaturated ring structure.

  Examples of the (meth) acrylate monomer having an aromatic ring and having an alkylene oxide modification number of 1 or more and 6 or less include EO adducts and PO adducts of polyhydric phenol acrylates.

  Examples of the polyhydric phenol include bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol PH, bisphenol Z and other bisphenols, and biphenol.

  Examples of the (meth) acrylate monomer having a saturated or unsaturated ring structure and having an alkylene oxide modification number of 1 or more and 6 or less include hydrogenated products of the above polyhydric phenol acrylates and dicyclodecane dimethanol dimers. Examples thereof include alkylene oxide adducts of diacrylates of diols having a carbon ring such as acrylate and cyclohexyl diacrylate.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, preferably modified with at least one of ethylene oxide and propylene oxide, and most preferably modified with ethylene oxide.

  When the modification number of the alkylene oxide is 1 or more and 6 or less, the obtained coating film has good crack resistance and solder heat resistance. The number of modification of alkylene oxide is the number of modification of alkylene oxide in one molecule of monomer, and specifically, the total number n of —R—O— (R is an alkylene group) in one molecule of monomer. .

  The number of alkylene oxide modifications is preferably 1 or more and 4 or less.

  (A) The (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 to 6 may be a polyfunctional (meth) acryloyl group-containing monomer (polyfunctional (meth) acrylate). A functional (meth) acryloyl group-containing monomer (monofunctional (meth) acrylate) may be used, but from the viewpoint of maintaining a low viscosity as a composition and the heat resistance of the coating after curing, ) An acryloyl group-containing monomer (bifunctional (meth) acrylate) is preferred. The (meth) acryloyl group is a term that generically refers to an acryloyl group and a methacryloyl group.

  (A) The (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 to 6 may be blended in an amount of 5 to 40 parts by mass per 100 parts by mass of the curable composition. preferable. By being in this concentration range, it is facilitated that the viscosity of the curable composition is in a range that can be used in the ink jet method, and the improvement of the reflow crack resistance and solder heat resistance of the obtained film is promoted. In addition, it is preferable to mix | blend in the quantity of 5 to 30 mass parts per 100 mass parts of curable compositions, More preferably, it is the quantity of 10 to 30 mass parts.

  As commercially available products, ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), BPE-80N (manufactured by Shin-Nakamura Chemical Industrial Co., Ltd.), BPE-100 (manufactured by Shin-Nakamura Chemical Industrial Co., Ltd.), BPE-4 (first) Kogyo Seiyaku Co., Ltd.), BPE-200 (Shin Nakamura Chemical Co., Ltd.), HBPE-4 (Daiichi Kogyo Seiyaku Co., Ltd.), Aronix M-208 (Toagosei Co., Ltd.) and the like.

[(B1) Bifunctional (meth) acrylate monomer having no cyclic skeleton and two or more alkylene glycol structures]
(B1) A bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures is added among diluents added to reduce the viscosity of the curable composition. The crack resistance at the time of reflow of the film obtained by this is improved. That is, this bifunctional (meth) acrylate monomer has (A) a cyclic skeleton, a (meth) acrylate monomer having an alkylene oxide modification number of 1 or more and 6 or less, and (B2) a cyclic skeleton described later. By combining with a bifunctional (meth) acrylate monomer having a monoalkylene glycol structure, the liquid resistance that can be used in the inkjet method is maintained, and the crack resistance and solder heat resistance of the obtained coating are improved.

  In the present invention, (B1) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures is, for example, an ester of di- or trialkylene glycol and (meth) acrylic acid. It is a certain bifunctional (meth) acryloyl group-containing monomer (bifunctional (meth) acrylate).

  Examples of the dialkylene glycol include diethylene glycol, dipropylene glycol, and dibutylene glycol. Examples of the trialkylene glycol include triethylene glycol, tripropylene glycol, and tributylene glycol.

  In addition, it is preferable that it is ester of dialkylene glycol and (meth) acrylic acid from a viewpoint of suppressing a viscosity with the viscosity suitable for an inkjet method.

  Specifically, (B1) a bifunctional (meth) acrylate monomer having neither an aromatic ring nor a saturated or unsaturated carbocycle and having a di- or trialkylene glycol structure includes diethylene glycol di (meth) acrylate, Examples include dipropylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and tributylene glycol di (meth) acrylate.

  As commercially available products, 2G (manufactured by Shin-Nakamura Chemical Co., Ltd.), 3G (manufactured by Shin-Nakamura Chemical Industrial Co., Ltd.), DPGDA (manufactured by Toyo Chemicals Co., Ltd.), T0948 (manufactured by Tokyo Chemical Industry Co., Ltd.), T2389 (Tokyo) Kasei Kogyo Co., Ltd.), Viscoat # 310HP (Osaka Organic Chemical Co., Ltd.) and the like.

  (B1) The bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures is blended in an amount of 20 to 50 parts by mass per 100 parts by mass of the curable composition. Is preferred.

[(B2) Bifunctional (meth) acrylate monomer not having a cyclic skeleton and having a monoalkylene glycol structure]
(B2) A bifunctional (meth) acrylate monomer having no cyclic skeleton and having a monoalkylene glycol structure is obtained by adding a diluent added to reduce the viscosity of the curable composition. This improves the solder heat resistance of the coated film. That is, this bifunctional (meth) acrylate monomer has (A) a cyclic skeleton, has a (meth) acrylate monomer having an alkylene oxide modification number of 1 or more and 6 or less, and does not have the (B1) cyclic skeleton, The combination with a bifunctional (meth) acrylate monomer having two or more alkylene glycol structures improves the reflow crack resistance and solder heat resistance of the resulting coating while maintaining the liquid properties that can be used in the inkjet method.

  In the present invention, (B2) the bifunctional (meth) acrylate monomer having no cyclic skeleton and having a monoalkylene glycol structure is, for example, a bifunctional (ester) of monoalkylene glycol and (meth) acrylic acid ( It is a (meth) acrylate monomer.

  The monoalkylene glycol structural moiety is preferably a linear or branched alkylene chain having 3 to 16 carbon atoms in one molecule, and particularly a linear alkylene chain having 6 to 9 carbon atoms. Preferably there is.

  Specifically, as the bifunctional (meth) acrylate monomer having (B2) both an aromatic ring and a saturated or unsaturated carbocycle and having a monoalkylene glycol structure, 1,3-butylene glycol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol acrylate, 1,10-decanediol diacrylate, 1,16-hexadecanediol Examples include diacrylate.

  Examples of commercially available products include HDDA (Daiichi Kogyo Seiyaku Co., Ltd.), A-NOD-N (Shin Nakamura Chemical Co., Ltd.), B1065 (Tokyo Kasei Kogyo Co., Ltd.), and Biscote # 195 (Osaka Organic Chemistry). Kogyo Co., Ltd.), A-DOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

  (B2) The bifunctional (meth) acrylate monomer having no cyclic skeleton and having a monoalkylene glycol structure is preferably blended in an amount of 10 to 30 parts by mass per 100 parts by mass of the curable composition. .

  In addition, (B2) a bifunctional (meth) acrylate having no cyclic skeleton and (B1) a bifunctional (meth) acrylate monomer having a monoalkylene glycol structure and having (B1) two or more alkylene glycol structures The monomer mass ratio is preferably 1.0 or more and 3.0 or less.

  When the mass ratio of the two is in the above range, (A) a cyclic skeleton, and a combination with a (meth) acrylate monomer having an alkylene oxide modification number of 1 to 6, the reflow crack resistance of the obtained film In addition, the solder heat resistance can be improved at a higher level.

  Further, (B1) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures and (B2) a bifunctional (meth) acrylate having no monoalkylene glycol structure and having no cyclic skeleton The mass ratio of the (meth) acrylate monomer having a cyclic skeleton (A) and having an alkylene oxide modification number of 1 to 6 with respect to the total amount of monomers is preferably 0.10 to 0.70.

  When the mass ratio of the three members is in the above range, the reflow crack resistance and solder heat resistance of the obtained coating can be realized at a higher level.

  Further, (A) a (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 or more and 6 or less, (B1) a bifunctional (meta) having no cyclic skeleton and having an alkylene glycol structure of 2 or more. The bifunctional (meth) acrylate monomer having a monoalkylene glycol structure without having an acrylate monomer and (B2) a cyclic skeleton may or may not contain a hydroxyl group in the molecule.

  Moreover, the curable composition used by this invention contains the following photoinitiators further.

[(C) Photopolymerization initiator]
The photopolymerization initiator is not particularly limited as long as it can polymerize (meth) acrylate by irradiation with energy rays, and a radical polymerization initiator can be used.

  Any radical photopolymerization initiator 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 photo radical polymerization initiator include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2- Acetophenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino Aminoacetophenones such as -1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloro Anthraquinones such as anthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 4,5-triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine, Organic halogen compounds such as 2,2,2-tribromoethanol and tribromomethylphenylsulfone; benzophenones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, and xanthones Down like; etc. 2,4,6-trimethylbenzoyl diphenylphosphine oxide.

  The above radical photopolymerization initiators can be used alone or in combination of two or more. Furthermore, in addition to these, tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine, etc. Photoinitiator aids can be used. In addition, a titanocene compound such as CGI-784 having an absorption in the visible light region (manufactured by BASF Japan) or the like can also be added to the photoradical polymerization initiator in order to accelerate the photoreaction. The components added to the radical photopolymerization initiator are not 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. These are not limited to photopolymerization initiators and photoinitiator aids, and can be used alone or in combination.

  The compounding quantity of a photoinitiator is 0.5-15 mass parts with respect to 100 mass parts of curable compositions, More preferably, it is 0.5-10 mass parts, More preferably, it is 1-10 mass parts.

  As a product name of what is marketed with a photoinitiator, Omnirad907, Omnirad127, Omnirad379 (all are the products made by IGM Resins), 2-isopropyl thioxanthone (made by Nippon Kayaku Co., Ltd.), etc. are mentioned, for example.

  Moreover, it is preferable that the curable composition of this invention contains a thermosetting component. By including a thermosetting component, it can be expected to improve the heat resistance such as adhesion (solder heat resistance and plating resistance) after soldering and plating of the obtained coating and suppression of cracks after heating.

  Known thermosetting components include amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, block isocyanate compounds, cyclocarbonate compounds, thermosetting components having a cyclic (thio) ether group, bismaleimide, carbodiimide resins, etc. These thermosetting resins can be mentioned. Among these, it is preferable to use a blocked isocyanate compound because of excellent storage stability.

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of either one of the three, four or five-membered cyclic (thio) ether groups or 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, a compound having a plurality of thioether groups in the molecule, that is, episulfide Examples thereof include resins.

  Examples of the polyfunctional epoxy compounds include epoxidized vegetable oils such as Adeka Sizer O-130P and Adeka Sizer O-180A manufactured by ADEKA; jER828 manufactured by Mitsubishi Chemical Co., EHPE 3150 manufactured by Daicel Chemical Industries, and Epicron 840 manufactured by DIC. Epototo YD-011 manufactured by Tohto Kasei Co., Ltd. and D.C. E. R. 317, Sumitomo Chemical ESA-011 manufactured by Sumitomo Chemical Co., Ltd. E. R. 330 bisphenol A type epoxy resin (both trade names); hydroquinone type epoxy resin, bisphenol F type epoxy resin such as YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., YSLV-120TE thioether manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Type epoxy resin: jERYL903 manufactured by Mitsubishi Chemical Corporation, Epicron 152 manufactured by DIC Corporation, Epotote YDB-400 manufactured by Tohto Kasei Co., Ltd., D.C. E. R. 542, Sumitomo Chemical ESB-400 manufactured by Sumitomo Chemical Co., Ltd. E. R. Brominated epoxy resins such as 711 etc. (all trade names); jER152 manufactured by Mitsubishi Chemical Corporation, D.C. E. N. 431DIC Epicron N-730, Toto Kasei Epototo YDCN-701, Nippon Kayaku EPPN-201, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, Asahi Kasei Kogyo Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235 (all trade names); biphenol novolak type epoxy resins such as NC-3000 manufactured by Nippon Kayaku; Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd., manufactured by Tohto Kasei Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F type epoxy resin; Toto Kasei Co., Ltd. Epototo ST-2004 (trade name) etc. hydrogenated bisphenol A type epoxy resins; Mitsubishi Glycidylamine type epoxy resin such as jER604 manufactured by Kagaku Co., Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (both trade names); Hydantoin type epoxy resin; Alicyclic epoxy trees such as Celoxide 2021 manufactured by the company (all are trade names) A trihydroxyphenylmethane type epoxy resin such as EPPN-501 manufactured by Nippon Kayaku Co., Ltd. (all trade names); YL-6056, YX-4000, YL-6121 manufactured by Mitsubishi Chemical Corporation (all trade names), etc. Bisylenol type or biphenol type epoxy resins or mixtures thereof; bisphenol S type epoxy resins such as Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name); Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by KK; tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) manufactured by Mitsubishi Chemical; TEPIC manufactured by Nissan Chemical Industries, Ltd. ( All are trade names) heterocyclic epoxy resins; Nigiri such as Bremer DGT manufactured by Nippon Oil & Fats Co., Ltd. Zyl phthalate resin; Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tohto Kasei; Naphthalene group-containing epoxy resin such as ESN-190 manufactured by Nippon Steel Chemical Co., Ltd .; HP-4032 manufactured by DIC; HP- manufactured by DIC Epoxy resin having dicyclopentadiene skeleton such as 7200; Glycidyl methacrylate copolymer epoxy resin such as CP-50S, CP-50M manufactured by NOF Corporation; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Examples thereof include, but are not limited to, polybutadiene rubber derivatives (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resins (for example, YR-102, YR-450 manufactured by Tohto Kasei Co., Ltd.), and the like. 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 bis Phenol ethers, 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.

  In addition, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate, etc. The monomer having both radical polymerization site (methacrylic group) and cationic polymerization site (oxetanyl site) in the molecule is both a photo-curing component and a thermo-curing component. Is preferably contained in the composition.

  Examples of such components include, in addition to polyfunctional oxetane compounds, for example, (meth) acryloyl group-containing bisphenol A type epoxy resin (product name, EA-1010LC, manufactured by Shin-Nakamura Chemical Co., Ltd.), 4-hydroxybutyl acrylate glycidyl ether (Product name, 4HBAGE, manufactured by Nippon Kasei Co., Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (product name, Cyclomer M100, manufactured by Daicel Corporation), and the like.

  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 which is friendly to the human body and the environment is preferably 0.2% or less.

  As these commercially available products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266 (all manufactured by Mitsui Cyanamid), Nicalak Mx-750, Mx-032 , Mx-270, Mx-280, Mx-290, Mx-706 (all manufactured by Sanwa Chemical Co., Ltd.). Such a thermosetting component may be used individually by 1 type, and may be used in combination of 2 or more type.

  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. By adding the polyisocyanate compound or the blocked isocyanate compound, the curability and the toughness of the resulting cured product can be improved.

  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, Examples thereof include 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, adducts, burettes and isocyanurates of the above-mentioned isocyanate compounds can be used.

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

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (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), TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Chemicals), 7950, 7951, 7960, 7961, 7982, 7990, 79 1,7992 (both Baxenden chemicals Co., Ltd.), 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.

  As for the compounding quantity of a thermosetting component, 1-30 mass parts is preferable per 100 mass parts of curable compositions of this invention. When the blending amount is 1 part by mass or more, the toughness and heat resistance of the coating film are further improved. On the other hand, if it is 30 mass parts or less, it can suppress that storage stability falls.

  Furthermore, the curable composition of this invention may contain the (meth) acrylate which has a hydroxyl group. By including the (meth) acrylate having a hydroxyl group, the adhesion of the obtained film to a conductor circuit metal or a plastic substrate is improved.

  As the (meth) acrylate having a hydroxyl group, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, 2-hydroxypropyl (Meth) acrylate etc. are mentioned. Commercially available products include Aronix M-5700 (trade name, manufactured by Toagosei Co., Ltd.), 4HBA, 2HEA, CHDMMA (named, product name manufactured by Nippon Kasei Co., Ltd.), BHEA, HPA, HEMA, HPMA (named, manufactured by Nippon Shokubai Co., Ltd.). Product name), light ester HO, light ester HOP, light ester HOA (above, product name manufactured by Kyoeisha Chemical Co., Ltd.) and the like. (B) The (meth) acrylate compound having a hydroxyl group can be used alone or in combination.

  Of these, 2-hydroxy-3-acryloyloxypropyl acrylate, 2-hydroxy-3-phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol Monoacrylate is preferably used. In addition, from the viewpoint of easy viscosity adjustment, a monofunctional (meth) acrylate compound is preferably used.

  The amount of the (meth) acrylate compound having a hydroxyl group is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the curable composition of the present invention.

  Furthermore, the curable composition of the present invention may contain a hyperbranched oligomer or a hyperbranched polymer. In the present invention, a multi-branched oligomer or polymer having an ethylenically unsaturated group is ethylenic in a multi-branched oligomer or polymer (referring to an oligomer or polymer having a plurality of branched chains in one molecule) skeleton. A compound having at least one unsaturated group. The ethylenically unsaturated group is derived from a functional group such as a (meth) acryloyl group, and may have a plurality of types of ethylenically unsaturated groups in one molecule. The (meth) acryloyl group is a concept including both an acryloyl group and a methacryloyl group.

  As a multi-branched oligomer and / or polymer having an ethylenically unsaturated group (hereinafter, also simply referred to as “multi-branched oligomer or polymer”), a compound having a dendrimer structure (dendritic structure) (hereinafter simply referred to as a dendrimer) Also a compound having a hyperbranched structure (hereinafter also simply referred to as a hyperbranch (oligomer or polymer)), a compound having a star structure (oligomer or polymer), and a compound having a graft structure (oligomer, The polymer is preferably a compound having a functional group having an ethylenically unsaturated bond, such as a (meth) acryloyl group.

  In the present invention, a dendrimer is a broad term for compounds having a structure in which branches and branches are spread radially. The specific kind of dendrimer is not particularly limited, and one or more kinds can be selected from known ones such as amidoamine-based dendrimers, phenyl ether-based dendrimers, and hyperbranched polyethylene glycol.

  The multi-branched oligomer or polymer generally has a weight average molecular weight (Mw) of 1000 to 20000, preferably 1000 to 8000. The weight average molecular weight (Mw) is a molecular weight in terms of polystyrene based on a molecular weight distribution curve based on gel permeation chromatography.

  The number of functional groups having an ethylenically unsaturated bond, particularly the number of (meth) acryloyl groups, in one molecule of the hyperbranched oligomer or polymer of the present invention is preferably 3 or more, particularly 4 to 30. Preferably, it is selected as long as the desired effect of the composition of the present invention is not impaired. In particular, since the photocurable composition of the present invention is used for inkjet, a composition having a functional group number of 30 or less that has a viscosity of 150 mPa · s or less at room temperature (25 ° C.) is used.

  The production method of the dendrimer is not particularly limited, and is a divergent method in which a molecule is bonded to a central core molecule for each generation to form a branch, a convergent method in which a branch portion synthesized in advance is bonded to a core molecule, and two or more reaction points A known production method such as a method of synthesizing in one step using a monomer ABx having a branched portion having B and a connecting portion having another reaction point A in one molecule can be employed.

  A commercially available dendrimer can also be used. For example, Etercure 6361-100 (Eternal Materials), Doublermer (DM) 2015 (Double Bond Chemical), SP1106 (Miwon Specialty Chemical), Biscote # 1000 (Manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  In addition, dendrimers are available from Iris Biotech, Kanto Chemical, Merk Millipore, QIAGEN, Sigma-Aldrich, Techno Chemical, Double Bond Chemical, Osaka Organic Chemicals, Hakuto, and others.

In the present invention, by using a multi-branched oligomer or polymer having an ethylenically unsaturated group, the adhesion between the curable composition and the substrate can be improved, and furthermore, the cured product can be given high hardness. . In addition, plating resistance with severe processing conditions can be improved.
Furthermore, since the multi-branched oligomer or polymer having an ethylenically unsaturated group has a relatively low viscosity even when the number of functional groups or the amount used is increased, it is significant for increasing the hardness of the curable composition. is there.

  The blending amount of the hyperbranched oligomer or polymer having an ethylenically unsaturated group is preferably 0.1 to 40% by mass relative to the total mass of the curable composition. The hardness of a coating film improves by setting it as 0.1 or more, and the viscosity increase of a hardening composition can be suppressed by setting it as 40 mass% or less.

  Moreover, the curable composition of this invention may contain the (meth) acrylate compound of 3 functional or more and 6 functional or less. By including a (meth) acrylate compound having 3 or more functional groups and 6 or fewer functional groups, an improvement in tackiness (dryness to touch) of the composition after photocuring is expected.

  Examples of the trifunctional to hexafunctional (meth) acrylate compounds include trimethylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, and epichlorohydrin-modified trimethylolpropane. Triacrylate, pentaerythritol tetraacrylate, tetramethylolmethane tetraacrylate, ethylene oxide modified phosphate triacrylate, propylene oxide modified phosphate triacrylate, epichlorohydrin modified glycerol triacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, or these Silsesquioki Polyfunctional acrylates represented by down-modified products, etc. or methacrylate monomers corresponding to these, include ε-caprolactone-modified trisacryloxyethyl isocyanurate. The amount of the trifunctional to hexafunctional (meth) acrylate compound is, for example, 1 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the curable composition of the present invention.

  The curable composition of the present invention may contain additives such as a defoaming / leveling agent, a thixotropy imparting agent / thickening agent, a coupling agent, a dispersant, and a flame retardant as necessary.

  Antifoaming and leveling agents include compounds such as silicone, modified silicone, mineral oil, vegetable oil, aliphatic alcohol, fatty acid, metal soap, fatty acid amide, polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene fatty acid ester, etc. Can be used.

  As thixotropy imparting agent / thickening agent, viscosity minerals such as kaolinite, smectite, montmorillonite, bentonite, talc, mica, zeolite, etc., fine silica, silica gel, amorphous inorganic particles, polyamide additives, modified urea additives, Wax-based additives can be used.

  By adding an antifoaming / leveling agent, a thixotropy imparting agent / thickening agent, the surface properties of the cured product and the properties of the composition can be adjusted.

  As the coupling agent, alkoxy group is methoxy group, ethoxy group, acetyl, etc., and reactive functional group is vinyl, methacryl, acrylic, epoxy, cyclic epoxy, mercapto, amino, diamino, acid anhydride, ureido, sulfide, Isocyanates and the like, for example, vinyl silane compounds such as vinyl ethoxylane, vinyl trimethoxysilane, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxylane, γ-aminopropyltrimethoxylane, Ν -Amino-silane compounds such as β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-ureidopropyltriethoxysilane, and γ-glycid Xypropyltrimethoxy Lan, epoxy-based silane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxylane, γ-glycidoxypropylmethyldiethoxysilane, mercapto-based silane compounds such as γ-mercaptopropyltrimethoxysilane, Silane coupling agents such as phenylamino silane compounds such as phenyl-γ-aminopropyltrimethoxysilane, isopropyl triisostearoylated titanate, tetraoctyl bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate , Isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tet (1,1-diallyloxymethyl-1-butyl) bis- (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrioctanoyl titanate, isopropyldimethacrylisostearoyl titanate, isopropyltristearoyl diacryl titanate , Titanate coupling agents such as isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, ethylenically unsaturated zirconate-containing compound, neoalkoxyzirconate-containing compound, Neoalkoxytris neodecanoyl zirconate, neoalkoxytris (dodecyl) benzenesulfur Honylzirconate, Neoalkoxytris (dioctyl) phosphate zirconate, Neoalkoxytris (dioctyl) pyrophosphate zirconate, Neoalkoxytris (ethylenediamino) ethylzirconate, Neoalkoxytris (m-amino) phenylzirconate, Tetra (2,2-diallyloxymethyl) butyl, di (ditridecyl) phosphito zirconate, neopentyl (diallyl) oxy, trineodecanoyl zirconate, neopentyl (diallyl) oxy, tri (dodecyl) benzene-sulfonyl zirconate, neopentyl (Diallyl) oxy, tri (dioctyl) phosphatozirconate, neopentyl (diallyl) oxy, tri (dioctyl) pyro-phosphatozirconate, neopentyl (dia Ru) oxy, tri (N-ethylenediamino) ethyl zirconate, neopentyl (diallyl) oxy, tri (m-amino) phenyl zirconate, neopentyl (diallyl) oxy, trimethacryl zirconate (, neopentyl (diallyl) oxy, tri Acrylic zirconate, dineopentyl (diallyl) oxy, diparaaminobenzoyl zirconate, dineopentyl (diallyl) oxy, di (3-mercapto) propionic zirconate, zirconium (IV) 2,2-bis (2-propenolatomethyl) ) Zirconate coupling agents such as butanolato, cyclodi [2,2- (bis-2-propenolatomethyl) butanolato] pyrophosphato-O, O, diisobutyl (oleyl) acetoacetylaluminate, alkylacetoacetate Diisopropylate aluminate coupling agents such like.

  Dispersants include polycarboxylic acid-based, naphthalene sulfonic acid formalin condensation-based, polyethylene glycol, polycarboxylic acid partial alkyl ester-based, polyether-based, polyalkylene polyamine-based polymeric dispersants, alkyl sulfonic acid-based, four Low molecular weight dispersants such as secondary ammonium series, higher alcohol alkylene oxide series, polyhydric alcohol ester series and alkylpolyamine series can be used.

  Flame retardants include hydrated metal such as aluminum hydroxide and magnesium hydroxide, red phosphorus, ammonium phosphate, ammonium carbonate, zinc borate, zinc stannate, molybdenum compound, bromine compound, chlorine compound, phosphate ester Phosphorus-containing polyol, phosphorus-containing amine, melamine cyanurate, melamine compound, triazine compound, guanidine compound, silicon polymer, and the like can be used.

  In order to adjust the polymerization rate and the polymerization degree, it is also possible to add a polymerization inhibitor and a polymerization retarder.

  Furthermore, in the curable composition of the present invention, a solvent may be used for adjusting the viscosity, but it is preferable that the addition amount is small in order to prevent a decrease in film thickness after curing. Moreover, it is more preferable that the solvent for viscosity adjustment is not included.

  For the purpose of coloring, a color pigment, a dye, or the like may be added to the curable composition of the present invention. As the color pigments and dyes, known ones represented by color indexes can be used. For example, Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 60, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, Pigment Green 7, 36, 3, 5, 20, 28, Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202, 110, 109, 139 179 185 93, 94, 95, 128, 155, 166, 180, 120, 151, 154, 156, 175, 181, 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111, 116, 167, 168, 169, 182, 183, 1 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198, Pigment Orange 1, 5, 13, 14, 16, 17 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73, Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147, 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268 269, 37, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53 : 2, 57: 1, 58: 4, 6 : 1, 63: 2, 64: 1, 68, 171, 175, 176, 185, 208, 123, 149, 166, 178, 179, 190, 194, 224, 254, 255, 264, 270, 272, 220 144, 166, 214, 220, 221, 242, 168, 177, 216, 122, 202, 206, 207, 209, Solvent Red 135, 179, 149, 150, 52, 207, Pigment Violet 19, 23, 29 32, 36, 38, 42, Solvent Violet 13, 36, Pigment Brown 23, 25, Pigment Black 1, 7, and the like. These coloring pigments and dyes are preferably added in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the curable composition.

  The curable composition of the present invention can be applied to printing by an inkjet method. In order to be applicable to printing by an ink jet method, it is preferable that the viscosity be jettable by an ink jet printer.

  Viscosity refers to the viscosity measured according to JIS K2283. Moreover, it is preferable that the viscosity of said curable composition for inkjet is 150 mPa * s or less at normal temperature (25 degreeC). As described above, the viscosity of the ink used in the ink jet printer is preferably about 20 mPa · s or less at the temperature at the time of application. However, if the viscosity is 150 mPa · s or less at room temperature, the above conditions can be satisfied by heating before coating or by heating during coating.

  Therefore, a pattern can be directly printed on a printed wiring board substrate or the like by the curable composition of the present invention.

  Furthermore, since the curable composition of the present invention does not cause a polymerization reaction at room temperature, it can be stably stored as a one-component curable composition.

  The curable composition of the present invention is supplied as an ink to an inkjet printer and used for printing on a substrate. Since the ink viscosity of the composition of the present invention is very low, printing and application by the ink jet method causes the pattern and characters printed and applied to the base material to spread and spread over a long period of time.

<Hardened product of curable composition>
The cured product of the curable composition of the present invention are obtained, for example, by photocuring a composition layer by performing 50mJ ^/ cm ² ~1000mJ ^/ cm 2 irradiation the composition layer immediately after the printing. The light irradiation is performed by irradiation with active energy rays such as ultraviolet rays, electron beams, and actinic rays, and preferably by ultraviolet rays.

  Ultraviolet irradiation in an inkjet printer can be performed, for example, by attaching a light source such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED to the side surface of the print head and performing scanning by moving the print head or the substrate. In this case, printing and ultraviolet irradiation can be performed almost simultaneously.

  When the cured product after photocuring contains a thermosetting component, the cured product is thermally cured by using a known heating means, for example, a heating furnace such as a hot air furnace, an electric furnace, or an infrared induction heating furnace. As heating conditions, it is preferable to heat at 130 to 170 ° C. for 5 to 90 minutes.

<Electronic component using cured product of curable composition as insulating cured film>
Thus, when the film (cured material) which consists of a curable composition pattern-printed on base materials, such as a board | substrate, is used as a soldering resist, it heats at the soldering process for mounting of components. Soldering may be performed by any of manual soldering, flow soldering, reflow soldering, etc., for example, in the case of reflow soldering, preheating at 100 ° C. to 140 ° C. for 1 to 4 hours, After that, heating is performed at 240 to 280 ° C. for about 5 to 20 seconds a plurality of times (for example, 2 to 4 times) to be subjected to a reflow process in which the solder is heated and melted. Parts are completed.

  In the present invention, the electronic component means a component used in an electronic circuit, and includes active components such as a printed wiring board, a transistor, a light emitting diode, and a laser diode, as well as passive components such as a resistor, a capacitor, an inductor, and a connector. Thus, the cured product of the curable composition of the present invention exhibits the effects of the present invention as these insulating cured coating films.

  In addition, when the substrate is a so-called rigid substrate, that is, a double-sided board in which wiring is printed on both sides or a multilayer board obtained by laminating the board, the board having a coating made of the curable composition is a plurality of times. It is subjected to a soldering process and repeatedly heated.

  According to the curable composition of the present invention, the obtained coating film (cured product) is free from cracks on the coating film even after receiving a thermal history assuming multiple soldering, and is a sufficient substrate. It has good mechanical properties expected as a solder resist applied on a rigid substrate.

  The curable composition of the present invention is excellent in plasticity, impact resistance, adhesion, chemical resistance, heat resistance (including crack resistance after heating, adhesion and hardness maintenance properties), insulation, and the like. Therefore, it can be applied to various uses, and there is no particular limitation on the application target. For example, it can be used for producing an etching resist, a solder resist, a marking resist, etc. of a printed wiring board using an ink jet method, and it can be suitably used as a solder resist requiring high heat resistance.

  It can also be used for applications such as UV molded material, stereolithography material, and 3D inkjet material.

  In addition, this invention is not limited to the structure and Example of said embodiment, A various deformation | transformation is possible within the range of the summary of invention.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated concretely, this invention is not limited only to these Examples. In the following description, “part” means part by mass unless otherwise specified.

[Examples 1-8 and Comparative Examples 1-2]
1. Preparation of composition Each component was mix | blended in the ratio (unit: mass part) shown in Table 1, and this was stirred with the dissolver.
Thereafter, dispersion was performed with 1 mm zirconia beads using a bead mill for 2 hours to obtain the compositions of the present invention (Examples 1 to 8) and comparative compositions (Comparative Examples 1 and 2).

  Product names and abbreviations in Table 1 are as follows.

ABE-300: EO-modified bisphenol A diacrylate (EO 3 mol adduct), manufactured by Shin-Nakamura Chemical Co., Ltd.
BPE-4: EO-modified bisphenol A diacrylate (EO 4 mol adduct), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
HBPE-4: EO-modified hydrogenated bisphenol A diacrylate (EO 4 mol adduct), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
BPE-10: EO-modified bisphenol A diacrylate (EO 10 mol adduct), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
DPGDA: Dipropylene glycol diacrylate, manufactured by Toyo Chemicals Corporation
A-NOD-N: 1,9-nonanediol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
HDDA: 1,6-hexanediol diacrylate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Laromer LR8863: EO-modified trimethylolpropane triacrylate (EO 6 mol adduct)
Omnirad 379: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, manufactured by Resins, IGM
ITX: 2-isopropylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by IGM Resins, Viscoat # 1000: Dendrimer polyester acrylate oligomer (a dendrimer based on a multi-branched (dendrimer type) polyester acrylate having an acrylate group at the terminal), Osaka Made by organic chemical industry
EA-1010LC: (Meth) acryloyl group-containing bisphenol A type epoxy resin (monofunctional), manufactured by Shin-Nakamura Chemical Co., Ltd.
BI7982: Trifunctional blocked isocyanate, manufactured by Baxenden chemmical
4HBA: 4-hydroxybutyl acrylate, manufactured by Nippon Kasei Co., Ltd. Melamine: manufactured by Nissan Chemical Co., Ltd. phthalocyanine blue: phthalocyanine blue pigment,
Chromophthalo Yellow AGR: Anthraquinone yellow pigment,
BYK-315N: Silicon-based surface conditioner, manufactured by Big Chemie Japan Co., Ltd. Composition viscosity: The viscosity at 50 ° C. measured according to JIS K2283 immediately after dispersion in a bead mill was determined according to the following criteria.

◎ Less than 15 mPa · s ○ More than 15 mPa · s and less than 150 mPa · s × Viscosity exceeding 150 mPa · s

2. 2. Production and evaluation of test substrate 2-1. Evaluation of crack resistance after high temperature treatment Using the obtained curable compositions of Examples and Comparative Examples, the following conditions

<Test board creation conditions>
Base material: Copper-clad laminate
Polishing: Buffing (Scotch brite SF (equivalent to # 600) and UEF (equivalent to # 1000))
Application: Applicator (manufactured by ERICHSEN), film thickness at application 30 μm
Temporary curing conditions: 300 mJ / cm ² , high pressure mercury lamp (HMW-713 manufactured by ORC) used as light source Thermal curing conditions: 150 ° C. for 60 minutes, heating device used DF610 (manufactured by Yamato Scientific Co., Ltd.) UV bump: 1000 mJ / Test substrates were prepared according to the use of cm ² and a high-pressure mercury lamp (HMW-713 manufactured by ORC) as a light source.

  Measure the temperature in the reflow furnace five times in advance under the same conditions as the reflow conditions according to the following conveyor speed and heat source set temperature using NISTEC-82C manufactured by Atec Techtron Co., Ltd. (see Fig. 1). It was confirmed that there was no. Thereafter, the test substrate obtained above was reflowed by air reflow under the same conditions.

Conveyor speed: 1.0m / min ≒ 1 zone (about 35cm) passes in about 20 seconds
Heat source set temperature: A. 210 ° C, B.I. 190 ° C., C.I. ~ F. 185 ° C., G.P. 265 ° C., H.P. 285 ° C., I.V. ~ J. Cooling process with fan

  The reflow treatment was performed up to 5 times, and from the second time onward, the presence or absence of cracks in the cured coating on the test substrate was confirmed each time the reflow treatment was performed. The results are shown in Table 2.

  As shown in Table 2, (A) a (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide variable of 1 to 6 and (B1) having no cyclic skeleton, having two or more alkylene glycol structures When used in combination with a bifunctional (meth) acrylate monomer having (B2) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having a monoalkylene glycol structure, after 5 thermal cycles of reflow The obtained coating did not cause cracks and had sufficient crack resistance. On the other hand, the comparative examples (Comparative Examples 1 and 2) having (A) a cyclic skeleton and having no (meth) acrylate monomer having an alkylene oxide modification number of 1 or more and 6 or less have cracks after reflow, The crack resistance after heating was not satisfactory.

2-2. Evaluation of characteristics of coating after high-temperature treatment Using the curable compositions of Examples and Comparative Examples obtained in “1. Preparation of composition”,
Each test substrate was produced under the same conditions as those in “2-1. Evaluation of crack resistance after high temperature treatment”.

  The prepared sample was immersed in a solder bath at 260 ° C. for 10 seconds in accordance with the method of JIS C-5012.

  Thereafter, the film characteristics were evaluated according to the following “2-2-1. Adhesiveness with a copper-clad laminate” and “2-2-2. Pencil hardness” for each test substrate after the solder immersion treatment.

2-2-1. Adhesiveness with copper-clad laminate A cross-cut tape peel test (JIS K 5600) was conducted using each of the prepared test substrates. Table 3 shows the percentage of the coating film remaining after the test as a percentage.

2-2-2. Pencil Hardness Pencil hardness on the surface of each test substrate prepared was measured according to JIS K 5600-5-4. Table 3 shows the pencil hardness of the coating film surface.

  As shown in Table 3, (A) a (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 to 6 and (B1) not having a cyclic skeleton, two or more alkylene glycol structures When used in combination with a bifunctional (meth) acrylate monomer having a (B2) bifunctional (meth) acrylate monomer having a monoalkylene glycol structure and having no cyclic skeleton, after three heat flows The film obtained also had good adhesion to the conductor on the substrate and had sufficient film hardness. On the other hand, in Comparative Example 1 and Comparative Example 2, the film hardness decreased after the soldering process, and the adhesion of the film to the conductor on the substrate decreased, and the film softened after the soldering process, and further from the conductor There is a risk of film peeling. Therefore, it is judged that the heat resistance of the coating film of the comparative example is lowered.

2-3. Evaluation of characteristics of coating after electroless plating treatment Furthermore, commercially available electroless nickel plating and electroless gold plating baths were applied to each test substrate prepared in “2-1. Evaluation of crack resistance after high temperature treatment”. Then, plating was performed on the cured film under the conditions of nickel 0.5 μm and gold 0.03 μm.

  Thereafter, the coating properties were evaluated according to the above “2-2-1. Adhesiveness with copper-clad laminate” and “2-2-2. Pencil hardness”. The results are shown in Table 4.

  As shown in Table 4, Examples 1 to 8 show good adhesion to the conductor of the formed film and sufficient hardness, while Comparative Examples 1 to 2 show the adhesion of the formed film to the conductor. Had fallen. That is, the comparative example (Comparative Example 1) having (A) a cyclic skeleton and having no (meth) acrylate monomer having an alkylene oxide modification number of 1 or more and 6 or less and (A) having a cyclic skeleton and 1 or more It was found that Comparative Example 2, which differs from the (meth) acrylate monomer having an alkylene oxide modification number of 6 or less only in the alkylene oxide modification number (= modification number 10), has low chemical resistance.

Claims (6)

(A) a (meth) acrylate monomer having a cyclic skeleton and having an alkylene oxide modification number of 1 to 6;
(B1) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures;
(B2) a bifunctional (meth) acrylate monomer that does not have a cyclic skeleton and has a monoalkylene glycol structure;
(C) a photopolymerization initiator;
A curable composition for inkjet printing comprising:   The amount of the (meth) acrylate monomer having a cyclic skeleton (A) per 100 parts by mass of the curable composition and having an alkylene oxide modification number of 1 or more and 6 or less is 5 parts by mass or more and 40 parts by mass or less. Item 2. A curable composition for inkjet printing according to Item 1.   (B1) a bifunctional (meth) acrylate monomer having no cyclic skeleton and having two or more alkylene glycol structures and (B2) a bifunctional (meth) acrylate monomer having a monoalkylene glycol structure without having a cyclic skeleton 3. The mass ratio of the (meth) acrylate monomer having a cyclic skeleton (A) and having an alkylene oxide modification number of 1 to 6 with respect to the total amount of 0.10 to 0.70. A curable composition for inkjet printing.   (B2) Bifunctional (meth) acrylate monomer having no cyclic skeleton and having a monoalkylene glycol structure (B1) Bifunctional (meth) acrylate monomer having no cyclic skeleton and two or more alkylene glycol structures The curable composition for inkjet printing according to any one of claims 1 to 3, wherein the mass ratio of the ink is 1.0 or more and 3.0 or less.   Hardened | cured material of the curable composition for inkjet printing as described in any one of Claims 1-4.   An electronic component having the cured product according to claim 5.

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