WO2021200268A1 - Curable composition, cured product, and electronic component - Google Patents

Abstract

[Problem] To provide: a curable composition that includes an AMA ester and produces cured products that are flexible, have low warpage, and adhere to conductor circuits; a cured product of the curable composition; and an electronic component that includes the cured product. [Solution] A curable composition that contains (A) a polymerizable monomer that is represented by formula (1) (in which R1 is a straight-chain, branched, or cyclic C1–4 hydrocarbon group that may include an ether linkage (and may also include a substituent)), (B) a compound selected from the group that consists of melamine and derivatives thereof, (C) a photopolymerization initiator, and (D) a thermosetting component. Cured products of the curable composition are flexible, have low warpage, and have high adhesion to conductor circuits.

Description

Curable compositions, cured products and electronic components

The present invention relates to a curable composition, a cured product thereof, and an electronic component containing the cured product, and more particularly to a curable composition suitable for an insulating material for a printed wiring board, and an electronic component containing the cured product and the cured product.

The α-allyloxymethylacryloyl group-containing ester (hereinafter, also referred to as AMA ester) polymerizes while being cyclized to form a main chain skeleton having a 5-membered ring ether structure having methylene groups arranged on both sides as a repeating unit. The cured product having this polymer has the characteristics of being excellent in heat-decomposability, adhesion to a resin substrate, and tough mechanical properties.

Patent Document 1 discloses a curable composition containing this AMA ester. Specifically, Patent Document 1 discloses a curable composition comprising a predetermined AMA ester, a bifunctional or higher photopolymerizable monomer, and a radical polymerization agent. This curable composition has excellent curability and is useful as an insulating material for an inkjet type printed wiring board.

Japanese Unexamined Patent Publication No. 2014-040585

As an insulating material for a printed wiring board, a curable composition to be applied on a circuit board is known, and such a curable composition is adjusted to various viscosities according to a coating method.
However, a curable composition for a printed wiring board is required to have strong adhesion to a conductor circuit, low warpage, and flexibility, and Patent Document 1 does not disclose these characteristics at all. No.

The present inventors sufficiently have the characteristics of adhesion, low warpage, and flexibility required for the cured product described in Patent Document 1 to be used as an insulating material for a printed wiring board. I found that there wasn't.

In view of the above problems, an object of the present invention is a curable composition having an AMA ester, which has adhesion to a conductor circuit of the cured product, low warpage, and flexibility, the cured product thereof, and the curing thereof. The purpose is to provide electronic components including things.

The present inventors have made diligent studies to achieve the above object. As a result, in addition to the α-allyloxymethylacrylic acid ester compound and the photopolymerization initiator, a compound selected from the group consisting of melamine and its derivatives and a thermosetting component are blended into the curable composition. We have found that high adhesion, low warpage and flexibility to the conductor circuit of the obtained cured product can be realized, and have completed the present invention.

That is, the object of the present invention is
(A) Equation (1)

(In the formula (1), R ¹ may be linear, branched or cyclic, and represents a hydrocarbon group having 1 or more and 4 or less carbon atoms which may contain an ether bond (provided that the hydrocarbon group has 1 or more and 4 or less carbon atoms). It may have a substituent in the hydrocarbon group))
With the polymerizable monomer represented by
(B) A compound selected from the group consisting of melamine and its derivatives, and
(C) Photopolymerization initiator and
(D) Thermosetting component and
It has been found that this is achieved with a curable composition containing.
Here, it is preferable that the curable composition of the present invention has a viscosity of 50 mPa · s or less at 50 ° C.

Further, the curable composition of the present invention preferably contains a compound having two or more (E) (meth) acryloyl groups, and a compound having two or more (E) (meth) acryloyl groups is (E1). ) It is more preferable to contain a compound having an aromatic ring and having two or more (meth) acryloyl groups.

Further, it is preferable that the (D) thermosetting component contains a latent thermosetting component, and it is further preferable that the latent thermosetting component is a blocked isocyanate compound.

Moreover, it is preferable that the curable composition of the present invention further contains (F) a phosphorus-based flame retardant.

Further, it is preferable that the curable composition of the present invention further contains a (G) ion scavenger.

Furthermore, the above object of the present invention can also be achieved by a cured product obtained from the curable composition of the present invention and an electronic component having the cured product.

According to the curable composition of the present invention, the obtained cured product has high adhesion to a conductor circuit, low warpage, and flexibility. Further, the cured product obtained from the curable resin composition of the present invention and the electronic component having the cured product also have high adhesion, low warpage and flexibility to the conductor circuit of the cured product. It becomes.

It is explanatory drawing of the MIT test performed on the cured film obtained from the curable composition.

<Curable composition>
The curable composition of the present invention is
(A) Equation (1)

(In the formula (1), R ¹ may be linear, branched or cyclic, and represents a hydrocarbon group having 1 or more and 4 or less carbon atoms which may contain an ether bond (provided that the hydrocarbon group has 1 or more and 4 or less carbon atoms). It may have a substituent in the hydrocarbon group))
(Hereinafter, also referred to as the polymerizable monomer of the formula (A) (1)) represented by
(B) A compound selected from the group consisting of melamine and its derivatives, and
(C) Photopolymerization initiator and
(D) Thermosetting component and
Have.

[Polymerizable monomer of formula (A) (1)]
The polymerizable monomer of the formula (A) (1) contained in the curable composition of the present invention can suppress the warp of the cured product after exposure, particularly on a flexible printed wiring board having flexibility. When the warp of the cured product becomes large, the entire flexible printed wiring board becomes cylindrical, which causes a problem that the curable composition cannot be applied at an appropriate position when recoating. Further, in the case of an inkjet printing application, if the flexible printed wiring board is warped, there arises a problem that the flexible printed wiring board comes into contact with the inkjet head. Then, there is also a problem that the warp becomes larger at the time of heat curing. However, since the curable composition of the present invention contains the polymerizable monomer of the formula (A) (1), it is possible to suppress the warp of the cured product after exposure and further suppress the warp after heat curing. ..
The polymerizable monomer of the formula (A) (1) contained in the curable composition of the present invention is, for example, the following formula a):

(In the formula a), R ¹ is the same as R ¹ in the formula (1), as represented by X · denotes the initiating radical or a growing radical), since the polymerization reaction while cyclization proceeds, It is considered that a main chain skeleton having a 5-membered ring ether structure having methylene groups arranged on both sides as a repeating unit is formed.

Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and a vinyl group. Examples thereof include an allyl group, a metalyl group, a crotyl group, a cyclopropyl group, a cyclobutyl group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group and a vinyloxyethyl group.

Examples of the substituent include a chain unsaturated hydrocarbon group such as a vinyl group, an allyl group, a metallicyl group and a crotyl group; an alkoxy group such as a methoxy group, an ethoxy group and a methoxyethoxy group; a methylthio group and an ethylthio group. Alkylthio group; acyl group such as acetyl group and propionyl group; acyloxy group such as acetyloxy group and propionyloxy group; alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; alkylthio such as methylthiocarbonyl group and ethylthiocarbonyl group Examples thereof include a carbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a ureido group; an amide group; a cyano group; and a trimethylsilyl group.

R ¹ is derived from the viewpoints of industrial ease of making the polymerizable monomer of the formula (A) (1) and reducing the viscosity of the polymerizable monomer of the formula (A) (1) to reduce the viscosity of the curable composition. , A chain saturated hydrocarbon group having 1 to 4 carbon atoms, a chain unsaturated hydrocarbon group having 1 to 4 carbon atoms, and a hydrocarbon group having an ether bond having 1 to 4 carbon atoms. Is preferable, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, allyl group, metallicyl group, crotyl group, methoxyethyl group, ethoxyethyl group and vinyl. Oxyethyl groups are more preferred.

Examples of the polymerizable monomer of the formula (A) (1) include methyl α-allyloxymethylacrylate, ethyl α-allyloxymethylacrylate, n-propyl α-allyloxymethylacrylate, and α-allyloxymethyl. Isopropyl acrylate, n-butyl α-allyloxymethylacrylate, sec-butyl α-allyloxymethylacrylate, tert-butyl α-allyloxymethylacrylate, vinyl α-allyloxymethylacrylate, α-allyloxy Allyl Methylacrylate, Metalyl α-allyloxymethylacrylate, Crotyl α-allyloxymethylacrylate, methoxymethyl α-allyloxymethylacrylate, methoxyethyl α-allyloxymethylacrylate, α-allyloxymethylacrylate Examples thereof include methoxypropyl, methoxybutyl α-allyloxymethylacrylate, ethoxymethyl α-allyloxymethylacrylate, ethoxyethyl α-allyloxymethylacrylate, and vinyloxyethyl α-allyloxymethylacrylate. These may be used alone or in combination of two or more.

The polymerizable monomer of the formula (A) (1) can be adjusted according to the methods described in, for example, JP-A-2014-040585, JP-A-2011-137123, and the like.

The blending amount of the polymerizable monomer of the formula (A) (1) is preferably 1 part by mass or more and 80 parts by mass or less, and more preferably 5 parts by mass or more and 60 parts by mass with respect to 100 parts by mass of the curable composition of the present invention. Parts or less, particularly preferably 5 parts by mass or more and 50 parts by mass or less.

[Compound selected from the group consisting of (B) melamine and its derivatives]
The curable composition of the present invention contains a compound selected from the group consisting of (B) melamine and its derivatives. Melamine and its derivatives are used to further improve properties such as heat resistance, in addition to improving the adhesion of the cured product to the conductor circuit.

(B) Compounds selected from the group consisting of melamine and derivatives thereof include, for example, guanamines such as acetguanamine and benzoguanamine; melamine; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2, Examples thereof include triazine derivatives such as 4-diamino-6-xylyl-S-triazine, and melamine is preferable.

(B) The compound selected from the group consisting of melamine and its derivatives can be used alone or in combination of two or more. When a compound selected from the group consisting of (B) melamine and a derivative thereof is blended in the curable composition of the present invention, the blending amount thereof is 100% by mass based on the total amount of the (D) thermocurable components described later. If so, it is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 15% by mass or less.

By setting the compounding amount of the compound selected from the group consisting of (B) melamine and its derivatives to 0.1% by mass or more and 20% by mass or less when the total amount of (D) thermosetting components is 100% by mass. , Good thermosetting can be realized while improving the storage stability of the curable composition.

[(C) Photopolymerization Initiator]
As the photopolymerization initiator, any compound that generates radicals by light, a laser, an electron beam, or the like and initiates a radical polymerization reaction can be used. Examples of the (C) photopolymerization 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, Acetophenones such as 2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2- Aminoacetophenones such as dimethylamino-1- (4-morpholinophenyl) -butane-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1- Anthraquinones such as chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; 2 , 4,5-Triarylimidazole dimer; riboflavin tetrabutyrate; thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole; 2,4,6-tris-s-triazine , 2,2,2-Tribromoethanol, organic halogen compounds such as tribromomethylphenylsulfone; benzophenones such as benzophenone, 4,4'-bisdiethylaminobenzophenone or xanthones; 2,4,6-trimethylbenzoyldiphenylphosphine Acylphosphines such as oxides; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl)] ) -9H-Carbazole-3-yl]-, 1- (O-acetyloxime) and other oxime esters can be mentioned.

The above (C) photopolymerization initiator can be used alone or in combination of two or more. In addition to these, light such as tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine Initiating aids can be used. Further, a titanocene compound of Omnirad 784 or the like (manufactured by IGM Resins BV), which absorbs in the visible light region, can also be added to the (C) photopolymerization initiator in order to promote the photoreaction. The components to be added to the photopolymerization initiator are not limited to these, and may be those that absorb light in the ultraviolet light or visible light region and radically polymerize an ethylenically unsaturated group such as a (meth) acryloyl group. For example, it is not limited to the photopolymerization initiator and the photoinitiator aid, and can be used alone or in combination of two or more. Twice

(C) Commercially available photopolymerization initiators include, for example, Omnirad 907, Omnirad 127, Omnirad 379EG (all manufactured by IGM Resins BV) and the like.

The photopolymerization initiator (C) may be a compound that initiates a cationic polymerization reaction. Examples of such (C) photopolymerization initiators include diphenyliodonium tetrafluoroboroate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrilium hexafluorophosphate, and commercially available products ( ADEKA's Optoma-SP-170 and SP-152, San-Apro's CPI-100P, CPI-101A, CPI-200K, CPI-210S and other sulfonium salt-based photocationic polymerization initiators, and BASF's Irgacure ( Registered trademark) 261 and the like.

The blending amount of the (C) photopolymerization initiator is preferably 0.2 to 25 parts by mass, and more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the curable composition of the present invention.

[(D) Thermosetting component]
In addition, the curable composition of the present invention contains (D) a thermosetting component. The thermosetting component (D) is different from the polymerizable monomer of the formula (A) (1), and by containing the (D) thermosetting component, in addition to improving the adhesion of the cured film to the conductor circuit, , Functionality such as heat resistance, plating resistance, flexibility, solvent resistance, and flame retardancy can be further improved.

As the (D) thermosetting component, for example, a known compound such as a blocked isocyanate compound, an epoxy compound, or an oxetane compound can be used.

Among them, in the present invention, a latent thermosetting component in which the functional group in the structure is protected by a protecting group can be preferably used. By using such a latent thermosetting component, it is possible to suppress an unintended reaction in the curable composition under unforeseen conditions and enhance the storage stability of the curable composition. In addition, such a curable composition is also excellent in inkjet printability at 50 ° C., and when cured, it can be easily deprotected by heating or the like, and a latent thermosetting component can be activated. can. In the present invention, the potential means a property that does not show activity at room temperature or a little heating condition, but is activated by heating at a high temperature of 80 ° C. or higher and shows thermosetting property.

Such a latent thermosetting component is preferably a blocked isocyanate compound. The blocked isocyanate compound is preferably a compound having a plurality of blocked isocyanate groups in one molecule. A blocked isocyanate group is a group in which an isocyanate group is protected by a reaction with a blocking agent and temporarily inactivated, and when heated to a predetermined temperature, the blocking agent is dissociated to generate an isocyanate group. do.

As the polyisocyanate compound having a plurality of isocyanate groups, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used.

Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and the like. Examples thereof include m-xylylene diisocyanate and 2,4-tolylen dimer.

Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate.

A specific example of the alicyclic polyisocyanate is bicycloheptane triisocyanate. In addition, the adduct form, the burette form, the isocyanurate form, and the like of the isocyanate compounds mentioned above can be mentioned.

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 oxime 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 Alcohol-based blocking agents such as ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetoaldoxime, acetoxime, methyl ethyl ketoxim, diacetyl monooxime and cyclohexane oxime. Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol, ethyl thiophenol; acid amide-based blocking agents such as acetate amide and benzamide; imides such as succinate imide and maleate imide. System blocking agents; amine blocking agents such as xylidine, aniline, butylamine, dibutylamine; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine; pyrazoles such as dimethylpyrazole Blocking agents and the like can be mentioned.

The blocked isocyanate compound may be commercially available, for example, Duranate TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Co., Ltd.), TrixeneBI7982: Blocked isocyanate (hexamethylene isocyanate (HDM) trimer, Blocking agents: dimethylpyrazole (DMP), Baxenden Chemicals) and the like.

The latent thermosetting component may be a reaction product obtained by reacting an amine compound such as imidazole or dicyandiamide with a hydroxyl group-containing compound, a cyclic ether group-containing compound, a carboxyl group-containing compound, or the like.

The blending amount of the thermosetting component (D) is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 5 parts by mass or more and 25 parts by mass or less per 100 parts by mass of the curable composition of the present invention. (D) When the blending amount of the thermosetting component is 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the curable composition of the present invention, the storage stability of the curable composition of the present invention is maintained. , Functionality such as heat resistance and plating resistance of the cured film can be further improved.

[(E) (Meta) compound having two or more acryloyl groups]
The curable composition of the present invention preferably contains a compound having two or more (E) (meth) acryloyl groups. (E) A compound having two or more (meth) acryloyl groups is a component that is cured by a photopolymerization reaction and is added to form a cured product. The compound having two or more (E) (meth) acryloyl groups is different from the polymerizable monomer of the formula (A) (1).

By having two or more (meth) acryloyl groups, good curability by a photopolymerization reaction can be obtained. Here, the (meth) acryloyl group is a general term for an acryloyl group and a meta-acryloyl group.

Further, in order to impart functionality as a solder resist such as good adhesion of the cured film (cured product) to the conductor circuit and film hardness even after the thermal history, that is, after the soldering treatment, (E) (meth). It is more preferable that the compound having two or more acryloyl groups contains a compound having (E1) an aromatic ring and two or more (meth) acryloyl groups.

Examples of the compound having (E1) aromatic ring and two or more (meth) acryloyl groups include (meth) acrylate of polyhydric phenol and its alkylene oxide adduct.

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 alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The number of alkylene oxides added is preferably 6 or less.

(E1) Commercially available compounds having an aromatic ring and having two or more (meth) acryloyl groups include ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), BPE-80N (manufactured by Shin-Nakamura Chemical Co., Ltd.), and the like. BPE-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-BPE-4 (manufactured by Shin-Nakamura Chemical Co., Ltd.), BPE-4 (manufactured by Dai-ichi Kogyo Pharmaceutical Co., Ltd.), BPE-10 (manufactured by Dai-ichi Kogyo Pharmaceutical Co., Ltd.) ), BPE-200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EBECRYL 150 (manufactured by Daicel Ornex Co., Ltd.) and the like.

Further, the compound having two or more (E) (meth) acryloyl groups is a compound having two low-viscosity (meth) acryloyl groups from the viewpoint of obtaining good curability while lowering the viscosity of the curable composition. Is preferably included. Here, in the compound having two or more (E) (meth) acryloyl groups, the low viscosity means that the viscosity at 50 ° C. is 50 mPa · s or less, and particularly the viscosity at 50 ° C. is 20 mPa · s or less.

Examples of the compound having two low-viscosity (meth) acryloyl groups include a bifunctional (meth) acryloyl group-containing monomer which is an ester of alkylene glycol and (meth) acrylic acid.

The alkylene glycol may be a monoalkylene glycol or one having a repeating structure of two or more alkylene glycols. Examples of the monoalkylene glycol include linear or branched alkylene diols having 3 to 16 carbon atoms, preferably 6 to 9 carbon atoms.

Examples of those having a repeating structure of two or more alkylene glycols include diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, tripropylene glycol, and tributylene glycol.

Specifically, examples of the compound having two low-viscosity (meth) acryloyl groups include diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, dibutylene glycol di (meth) acrylate, and triethylene glycol di. (Meta) acrylate, tripropylene glycol di (meth) acrylate, tributylene glycol di (meth) acrylate, 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 diacrylate and the like can be mentioned.

Commercially available products of compounds having two low-viscosity (meth) acryloyl groups include 2G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 3G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPGDA (manufactured by Daicel Ornex), and T0948 ( Tokyo Chemical Industry Co., Ltd., T2389 (Tokyo Chemical Industry Co., Ltd.), Viscoat # 310HP (Osaka Organic Chemical Industry Co., Ltd.), PE-200 (Daiichi Kogyo Seiyaku Co., Ltd.), PE-300 (Daiichi) Industrial Pharmaceutical Co., Ltd.), HDDA (Dycel Ornex Co., Ltd.), LC9A (Daiichi Kogyo Pharmaceutical Co., Ltd.), A-NOD-N (Shin-Nakamura Chemical Industry Co., Ltd.), B1065 (Tokyo Chemical Industry Co., Ltd.) (Manufactured by), 1,9-NDA (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like.

Further, in order to further improve the curability by the photopolymerization reaction, it is preferable that the compound having two or more (E) (meth) acryloyl groups contains a compound having three or more (meth) acryloyl groups.

Examples of the compound having three or more (meth) acryloyl groups include trimethylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, and epichlorohydrin-modified trimethylolpropane triacrylate. Acrylate, pentaerythritol tetraacrylate, tetramethylolmethanetetraacrylate, ethyleneoxide-modified phosphoric acid triacrylate, propylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, or these. Examples thereof include polyfunctional acrylates typified by silsesquioxane-modified products, metaacrylate monomers corresponding thereto, and εcaprolactone-modified trimethyloloxyethyl isocyanurate.

The compound having three or more (meth) acryloyl groups may be a multi-branched oligomer or polymer.

The compound having two or more (meth) acryloyl groups is preferably 10 parts by mass or more and 90 parts by mass or less, and preferably 10 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the curable composition of the present invention. It is particularly preferably 15 parts by mass or more and 75 parts by mass or less.

(E) When the compound having two or more (meth) acryloyl groups is 10 parts by mass or more per 100 parts by mass of the curable composition of the present invention, the compatibility is improved, the compound is uniformly dispersed, and good coating film characteristics are obtained. Is obtained, and when it is 90 parts by mass or less, the effect of improving heat resistance can be obtained.

[(F) Phosphorus flame retardant]
The curable composition of the present invention preferably contains a known and commonly used (F) phosphorus-based flame retardant for the purpose of improving the flame retardancy of the obtained cured product.

Examples of the phosphorus-based flame retardant include a phosphoric acid ester and a condensed phosphoric acid ester, a phosphorus-containing compound having a phenolic hydroxyl group, a phosphazene compound, a phosphinic acid metal salt, and the following general formula (2).

(In the formula (2), R ² , R ³ and R ⁴ each independently represent a substituent other than a halogen atom).

In the above general formula (2), R ² and R ³ are preferably hydrogen atoms or alkyl groups having 1 or more and 4 or less carbon atoms, and R ⁴ may be substituted with hydrogen atoms or cyano groups. A good alkyl group having 1 or more and 4 or less carbon atoms, a 2,5-dihydroxyphenyl group, or a 3,5-di-t-butyl-4-hydroxyphenyl group is preferable, but is limited thereto. It's not a thing.

Commercially available products of the compound represented by the above general formula (2) include HCA, SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sanko Co., Ltd.) and the like.

The phosphorus-containing compound having a phenolic hydroxyl group, in the general formula (2), R ⁴ may be mentioned those wherein a phenyl group substituted with a hydroxyl group. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.

Examples of the phosphinic acid metal salt include the following structural formula (3).

(In equation (3),
R ₁ and R ₂ represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms, respectively.
M represents calcium, aluminum or zinc, m = 3 when M represents aluminum, and m = 2 when M represents other metals)
Those having a structure represented by are preferable.

More preferably, it is a compound having a structure in which M represents aluminum in the formula (3).

By using a metal phosphinic acid salt, flame retardancy can be improved without impairing the flexibility of the cured film.

Specific examples of the phosphinic acid constituting the phosphinic acid metal salt include phosphinic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi (methylphosphinic acid), benzene-1, Examples thereof include 4- (dimethylphosphinic acid), methylphenylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid and mixtures thereof.

Examples of commercially available products include Exolit OP 1240, 1240, 1312, 1400, 930, 945TP, and OP-935.

The phosphazene compound is preferably a compound having a phenoxy group and a phosphazene structure substituted with any one of a cyano group (-CN), a hydroxyl group (-OH) and a methyl group. In particular, it has a hexaphenoxycyclotriphosphazene structure as a basic skeleton, and at least two of the six phenoxy groups in the structure are substituted with a cyano group (-CN) or a hydroxyl group (-OH). preferable.

In a preferred embodiment, only one of the two phenoxy groups attached to the phosphorus atom in the hexaphenoxycyclotriphosphazene structure is substituted with and thus substituted with one cyano group (-CN). It is a structure having two hexaphenoxycyclotriphosphazene structures as a whole.

In yet another preferred embodiment, the two phenoxy groups attached to the phosphorus atom in the hexaphenoxycyclotriphosphazene structure are both substituted with one cyano group (-CN), and the phenoxy group thus substituted. Is a structure having all six hexaphenoxycyclotriphosphazene structures as a whole.

In yet another preferred embodiment, only one of the two phenoxy groups attached to the phosphorus atom in the hexaphenoxycyclotriphosphazene structure is substituted with one hydroxyl group (-OH) and thus thus. It is a structure having three substituted phenoxy groups as a whole hexaphenoxycyclotriphosphazene structure.

More preferably, the cyclic phosphazene compound has the following structure:

or

or

It has one of the above structures.

Examples of commercially available products of preferable phosphazene compounds include FP-300B, FP-300, and SPH-100 (all manufactured by Fushimi Pharmaceutical Co., Ltd.).

(F) One type of phosphorus-based flame retardant may be used alone, or two or more types may be used in combination. When the phosphorus-based flame retardant (F) is blended, the blending amount is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass, with respect to 100 parts by mass of the curable composition of the present invention. It is 40 parts by mass or less. In particular, the blending amount of the phosphorus-based flame retardant (F) is preferably 0.1 to 10%, more preferably 1 to 5%, as the phosphorus content in the curable composition of the present invention. When the phosphorus-based flame retardant (F) is blended within the above range, flame retardancy can be effectively imparted while maintaining heat resistance and low warpage. In the curable composition of the present invention, may be used boric acid metal salts Firebrake ZB such as flame retardants (zinc borate compound _{(2ZnO · 3B 2 O 3 ·} 3.5H 2 O).

[(G) Ion scavenger]
The curable composition of the present invention preferably contains a known and commonly used (G) ion scavenger in order to improve insulation reliability such as ion migration resistance.

(G) As the ion trapping agent, an inorganic cation trapping agent that traps cations by ion exchange, an inorganic anion trapping agent that traps anions by ion exchange, and both cations and anions by ion exchange are used. Examples thereof include an inorganic amphoteric trapping agent, and an inorganic amphoteric trapping agent is preferable.

The (G) ion scavenger contains at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, and bismuth. In particular, two or more oxidative hydrates or hydroxides of these components are preferable, and two or more oxidative hydrates or hydroxides selected from the group consisting of zirconium, magnesium and aluminum are more preferable. Of these, hydrotalcite, which is a three-component oxidative hydrate of magnesium, aluminum and zirconium, bismuth, and a two-component oxidative hydrate of zirconium and a hydroxide containing magnesium and aluminum, is preferable. The ion scavenger may be used alone or in combination of two or more.

Hydrotalcite is represented by the following formula (1).

Mg _a Al _b (OH) _c (CO ₃ ) _d · nH ₂ O ・ ・ ・ (1)
(In the formula (1), a, b, c, and d are positive numbers and satisfy 2a + 3b-c-2d = 0. Further, n indicates the number of hydration, which is 0 or a positive number, which is preferable. Is 1 to 5.)

In the formula (1), one in which a part of Mg is replaced with another divalent metal ion can also be preferably used. Among other divalent metal ions, Zn is particularly preferable.

Specific examples of the hydrotalsite are not particularly limited, but for example, Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · nH ₂ O, Mg ₅ Al _1.5 (OH) _12.5 CO ₃ · nH ₂ O, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ · nH ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃ · nH ₂ O, Mg _4.3 Al ₂ (OH) _12.6 CO ₃・ NH ₂ O, Mg _2.5 Zn ₂ Al ₂ (OH) ₁₃ CO ₃・ nH ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃・ nH ₂ O, Mg _4.2 Al ₂ ( OH) _12.4 CO ₃ · nH ₂ O, Mg ₄ Al ₂ (OH) ₁₂ CO ₃ · nH ₂ O, etc. 5), and among them, Mg _4.3 Al ₂ (OH) _12.6 CO ₃ · nH ₂ O is preferable.

As the hydrotalcite represented by the formula (1), a / b is preferably 1.5 or more and 5 or less, more preferably 1.7 or more and 3 or less, and 1.8 or more and 2.5. The following is more preferable.

The average particle size of the (G) ion scavenger is usually 5 μm or less, preferably 1 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and further preferably 0.3 μm or more.

The average particle size of the ion scavenger can be measured by the dynamic light scattering method. Specifically, it can be measured by creating a particle size distribution of the ion scavenger on a volume basis with a dynamic light scattering type particle size distribution measuring device and using the median diameter (D50) as the average particle size. As the measurement sample, an ion scavenger dispersed in water by ultrasonic waves can be preferably used. As the dynamic light scattering type particle size distribution measuring device, Nanotrac Wave II UT151 or the like manufactured by Microtrac Bell can be used.

As the ion scavenger (G), a commercially available product may be used, for example, IXEPLAS-A1, IXEPLAS-A2, IXEPLAS-A3, IXEPLAS-B1 manufactured by Toagosei Co., Ltd., DHT-4A, DHT manufactured by Kyowa Chemical Industry Co., Ltd., etc. -4A-2, DHT-4C and the like can be mentioned.

When the (G) ion scavenger is blended, the blending amount thereof is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the curable composition of the present invention. It is 0.02 parts by mass or more and 5 parts by mass or less, and more preferably 0.03 parts by mass or more and 3 parts by mass or less. When the blending amount of the ion scavenger is within the above numerical range, insulation reliability and adhesion after high temperature and high humidity can be improved without lowering flexibility, low warpage, and flame retardancy.

[Compounds having (meth) acryloyl group and hydroxyl group (excluding compounds having two or more (meth) acryloyl groups)]
Further, the curable composition of the present invention preferably contains a compound having a (meth) acryloyl group and a hydroxyl group. By containing a compound having a (meth) acryloyl group and a hydroxyl group, the adhesion between the obtained cured film and the conductor and the substrate is improved.

Examples of the compound having a (meth) acryloyl group and a hydroxyl group include 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, and 1,4-cyclohexanedimethanol mono. Meta) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, Examples thereof include 2-hydroxypropyl (meth) acrylate. Commercially available products include Aronix M-5700 (trade name manufactured by Toagosei Co., Ltd.), 4HBA, 2HEA, CHDMMA (above, product name manufactured by Kyoeisha Chemical Co., Ltd.), BHEA, HPA, HEMA, HPMA (above, manufactured by Nippon Catalyst 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. The compound having a (meth) acryloyl group and a hydroxyl group can be used alone or in combination of two or more.

Of these, especially 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. Further, from the viewpoint of ease of viscosity adjustment, a compound having one (meth) acryloyl group is preferably used.

The blending amount of the compound having a (meth) acryloyl group and a hydroxyl group is preferably 1 to 15 parts by mass, more preferably 1 to 10 parts by mass, and particularly, per 100 parts by mass of the curable composition of the present invention. It is preferably 2 to 8 parts by mass.

Additives such as antioxidants, antifoaming / leveling agents, thixotropy-imparting agents / thickening agents, coupling agents, dispersants, polymerization retarders, and colorants are added to the curable composition of the present invention, if necessary. It can be contained.

Further, although a solvent may be used for adjusting the viscosity of the curable composition of the present invention, it is preferable that the amount added is small in order to prevent a decrease in film thickness after curing. Further, it is more preferable that the solvent for adjusting the viscosity is not contained.

The curable composition of the present invention is preferably applied to printing by an inkjet method. In order to make it applicable to printing by the inkjet method, it is preferable that the viscosity is such that it can be ejected by an inkjet printer.

The viscosity of the curable composition of the present invention is preferably 50 mPa · s or less at 50 ° C., more preferably 20 mPa · s or less at 50 ° C., and 15 mPa · s or less at 50 ° C. Is particularly preferable. The viscosity is 50 ° C., 100 rpm, 30 seconds value according to the viscosity measurement method using a 10-cone-plate type rotational viscometer of JIS Z8803: 2011, and the cone plate type viscosity using 1 ° 34'x R24 as the cone rotor. It is a value measured by a meter (TVE-33H, manufactured by Toki Sangyo Co., Ltd.).

Therefore, the curable composition of the present invention can directly print a pattern on a substrate or the like for a printed wiring board by an inkjet printing method.

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

When the viscosity of the curable composition of the present invention is 50 mPa · s or less at 50 ° C., it can be supplied as ink to an inkjet printer and can be used for printing on a substrate.

<Curing product obtained by curable composition>
The cured product obtained by the curable composition of the present invention is, for example, photocuring the composition layer immediately after printing by irradiating the composition layer with an active energy ray ^{of 50 mJ / cm 2} to 1000 mJ / cm ^2. Obtained at. The activation energy ray irradiation is performed by irradiation with active energy rays such as ultraviolet rays, electron beams, and chemical rays, preferably by ultraviolet irradiation.

Ultraviolet irradiation in an inkjet printer can be performed by, for example, 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 scanning by moving the print head or the substrate. In this case, printing and ultraviolet irradiation can be performed almost at the same time.

The cured product after photocuring 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 the heating conditions, it is preferable to heat at 130 ° C. to 170 ° C. for 5 minutes to 90 minutes.

The cured product obtained by the curable composition of the present invention is also excellent in flexibility, and is therefore particularly suitable as a solder resist for a flexible printed wiring board.

Examples of the substrate of the flexible printed wiring board include a film made of glass polyimide, polyimide, polyethylene terephthalate, liquid crystal polymer, polycarbonate, and the like.

<Electronic components with a cured product of a curable composition>
When a cured film made of a curable composition with a pattern printed on a substrate in this way is used as a solder resist, it is heated in a soldering step for mounting components. Soldering may be performed by hand soldering, flow soldering, reflow soldering, or the like. For example, in the case of reflow soldering, preheating at 100 ° C. to 140 ° C. for 1 to 4 hours is required. After that, it is subjected to a reflow process of heating and melting the solder by repeating heating at 240 to 280 ° C. for about 5 to 20 seconds a plurality of times (for example, 2 to 4 times). The part is completed.

In the present invention, the electronic component means a component used in an electronic circuit, and includes active components such as printed wiring boards, transistors, light emitting diodes, and laser diodes, as well as passive components such as resistors, capacitors, inductors, and connectors. The cured product of the curable composition of the present invention exerts the effect of the present invention as these insulating cured films.

The curable composition of the present invention can be easily reduced in viscosity, has excellent coatability, and has little warpage after photocuring. Further, it is flexible even after curing, and is excellent in adhesion to a substrate, flame retardancy, solder heat resistance, plating resistance, and solvent resistance, so that it can be applied to various applications, and there is no particular limitation on the application target. For example, it can be used for manufacturing etching resists, solder resists, marking inks, etc. for printed wiring boards using an inkjet method, and is preferably used as a solder resist for flexible printed wiring boards, which require high heat resistance and flexibility. be able to.

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

The present invention is not limited to the configuration and examples of the above-described embodiment, and various modifications can be made within the scope of the gist of the invention.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following, unless otherwise specified, "parts" shall mean parts by mass.

<1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3>
Each component was blended at the ratio (unit: parts by mass) shown in Table 1 below, and this was stirred with a dissolver. Then, dispersion was carried out with zirconia beads using a bead mill for 2 hours to obtain a curable composition of the present invention (Examples 1 to 8) and a curable composition of Comparative Examples (Comparative Examples 1 to 3). As a bead mill, a conical type K-8 (manufactured by Buhra) was used and kneaded under the conditions of a rotation speed of 1200 rpm, a discharge rate of 20%, a bead particle size of 0.65 mm, and a filling rate of 88%.

* 1: Methyl α- (allyloxymethyl) acrylate (FX-AOMA: manufactured by Nippon Shokubai Co., Ltd.)
* 2: Trimethylolpropane triacrylate (A-TMPT: manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
* 3: 1,9-Nonanediol diacrylate (1,9-NDA: manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
* 4: Dipropylene glycol diacrylate (DPGDA: manufactured by Toyo Chemicals Co., Ltd.)
* 5: Ethoxylated bisphenol A diacrylate (A-BPE-10: manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
* 6: 4-Hydroxybutyl acrylate (4HBA: manufactured by Kyoeisha Chemical Co., Ltd.)
* 7: Trifunctional blocked isocyanate (BI7982: manufactured by Baxenden chemmical)
* 8: Melamine (manufactured by Nissan Chemical Industries, Ltd.)
* 9: 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (Omnirad 379: manufactured by IGM Resins)
* 10: Phosphazene compound (phosphorus content 12.5%) (FP-300B: manufactured by Fushimi Pharmaceutical Co., Ltd.)
* 11: Metallic phosphinic acid salt (phosphorus content 23%) (OP935: manufactured by Clariant Chemicals)
* 12: Phosphorus-containing compound having a phenolic hydroxyl group (phosphorus content 9.6%) (HCA-HQ: manufactured by Sanko Co., Ltd.)
* 13: Ion scavenger containing Mg-based compound, Al-based compound and Zr-based compound (IXEPLAS-A1: manufactured by Toagosei Co., Ltd.)
* 14: Phthalocyanine-based blue pigment (Pigment Blue 15: 3)
* 15: Anthraquinone-based yellow pigment (Pigment Yellow147)

<2. Evaluation ＞
Above <1. The viscosities of each of the curable compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 3> were evaluated as follows. In addition, prepare a test sample as shown below, and prepare a test sample, and applyability, warpage after exposure, flexibility (MIT test), solder heat resistance, solvent resistance, electroless gold plating resistance, flame retardancy and high temperature and humidity. Post-adhesion was evaluated. The results are shown in Table 2.

(1) Viscosity <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> For each curable composition obtained, the values were set at 50 ° C., 100 rpm, and 30 seconds, and the value was set to 1 ° 34'x R24 as a cone rotor. It was measured with a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) using the above, and evaluated according to the following criteria.

⊚: 10 mPa · s or less ○: 10 mPa · s more than 20 mPa · s or less ×: 20 mPa · s more than

(2) Conditions for forming a cured film <1. Each curable composition obtained in Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> was applied using an inkjet printing apparatus CPS6151 (manufactured by Microcraft). As the array, KM1024iSHE (manufactured by Konica Minolta, coating droplet amount 6 pL, number of nozzles 1024, head temperature 50 ° C.) was used. ^{Photocuring was performed at 300 mJ / cm 2} using SGHUV-UN-L042-B (manufactured by Microcraft, LED light source, wavelength 365 nm) as a light source. After that, a hot air circulation type drying furnace DF610 (manufactured by Yamato Kagaku Co., Ltd.) was used as a heating device, and the main curing was performed at 150 ° C. for 60 minutes.

(3) Applyability <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained was treated with sulfuric acid using an inkjet printing device CPS6151 (manufactured by Microcraft Co., Ltd.). It was applied on the copper surface of M (registered trademark) M (manufactured by Nittetsu Chemical & Materials Co., Ltd.) with a coating thickness of 20 μm. The surface of the cured film was visually observed and evaluated according to the following criteria.

◯: Uniform coating and smooth surface Δ: Full coating but streaks in the head operation direction ×: Part of the cured film is missing What is

(4) Warpage after exposure <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained was subjected to a photocuring condition of 800 mJ / cm ^{2 using an inkjet printing device CPS6151 (manufactured by Microcraft).} Then, one-sided coating was applied to Sulfuric acid-treated Kapton (registered trademark) 200H (manufactured by Toray DuPont). The obtained laminated body of the cured film after exposure was cut into 5 cm x 5 cm (length x width) to prepare a sample (film thickness: 15 μm). After exposure, each sample was allowed to stand on a horizontal work table for 30 minutes with the cured film surface as the upper surface, and the heights of the four edges of the sample raised from the work table were measured with a ruler, and the average value of the heights of the four ends was measured. Asked. The same test was performed three times for each sample, and the average value of the three tests was calculated and evaluated according to the following criteria.

⊚: The average value of the total heights of the four ends is 5 mm or less ○: The average value of the total heights of the four ends exceeds 5 mm and less than 10 mm ×: The average value of the total heights of the four ends is 10 mm or more

(5) Flexibility (MIT test)
Above <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> was used to form a circuit pattern of each curable composition obtained by CP56151 manufactured by Microcraft Co., Ltd. with a sulfuric acid-treated copper thickness of 12 μm. It was applied onto a substrate having a polyimide of 25 μm. Then, a cured film having a thickness of 20 μm was formed according to the above “(2) Conditions for forming a cured film”. The obtained cured film was subjected to a MIT test (R = 0.38 mm) based on JIS P8115 to evaluate its flexibility.

Specifically, as shown in FIG. 1, the test piece 1 is mounted on the apparatus, the test piece 1 is vertically attached to the clamp 2 with the load F (0.5 kgf) applied, and the bending angle α is set. Bending was performed at 135 degrees and a speed of 175 cpm, and the number of reciprocating bends (times) until breaking was measured. The test environment was 25 ° C., and the radius of curvature was R = 0.38 mm. The evaluation criteria are as follows.

⊚: 150 times or more ○: 100 to 149 times Δ: 50 to 99 times ×: 49 times or less

(6) Solder heat resistance <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Using an inkjet printing device CPS6151 (manufactured by Microcraft Co., Ltd.), each curable composition was subjected to photocuring conditions of 800 mJ / cm ² The coating was applied on a circuit pattern substrate having a copper thickness of 12 μm and a polyimide of 50 μm treated with sulfuric acid. Then, a cured film having a thickness of 20 μm was formed according to the above “(2) Conditions for forming a cured film”. A rosin-based flux is applied to the obtained evaluation substrate, immersed in a solder bath set at 260 ° C. in advance for 5 seconds once or twice, the flux is washed with a modified alcohol, and then a cross-cut tape peel test is performed. This was performed and the swelling and peeling of the cured film were evaluated. The judgment criteria are as follows.

⊚: No peeling was observed in the cured film even when the film was immersed twice for 5 seconds and a peel test was performed with cellophane tape (registered trademark).
◯: Even if the film was immersed once for 5 seconds and the peel test was performed with cellophane tape (registered trademark), no peeling was observed in the cured film.
X: When the film is immersed for 5 seconds × 1 time, the cured film swells and peels off.

(7) Solvent resistance <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Using an inkjet printing device CPS6151 (manufactured by Microcraft Co., Ltd.), each curable composition was subjected to photocuring conditions of 800 mJ / cm ² On the copper surface of Espanex (registered trademark) M (manufactured by Nittetsu Chemical & Materials Co., Ltd.) that has been treated with sulfuric acid, heat it in a hot air circulation type drying oven at 150 ° C. for 60 minutes to a thickness of 20 μm. A cured film was obtained. The state of the cured film after being immersed in propylene glycol monomethyl acetate for 30 minutes was evaluated. The evaluation criteria are as follows.

◯: No change is observed △: Slightly changed ×: Significant change

(8) Electroless gold plating resistance <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Sulfuric acid-treated copper thickness of 12 μm using an inkjet printing device CPS6151 (manufactured by Microcraft). , Polyimide 50 μm was applied onto a circuit pattern substrate. Then, a cured film having a thickness of 20 μm was formed according to the above “(2) Conditions for forming a cured film”. The obtained evaluation substrate was gold-plated using a commercially available electroless nickel plating bath and an electroless gold plating bath under the conditions of nickel 5 μm and gold 0.03 μm, and the surface condition of the cured film was observed. The evaluation criteria are as follows.

◯: No change was observed ×: Significant whitening or cloudiness occurred

(9) Flame retardancy <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Using an inkjet printing apparatus CPS6151 (manufactured by Microcraft), FR-4 (0.8 mmt) was used to prepare each curable composition. ) Double-sided coating was applied on the substrate. Then, after that, a cured film was formed according to the above "(2) Conditions for forming a cured film" (the coating film thickness on each surface is 20 μm). The obtained cured film was subjected to a thin lumber vertical combustion test conforming to the UL94 standard. The evaluation criteria are as follows.

⊚: Passed V-0 and burned time of each sample less than 3 seconds ○: Passed V-0 and burned time of each sample more than 3 seconds and less than 7 seconds V-0: Passed V-0 , Burning time of each sample is more than 7 seconds and less than 10 seconds Not: V-0 failed

(10) Adhesion after high temperature and high humidity <1. Preparation of curable compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained was treated with sulfuric acid using an inkjet printing device CPS6151 (manufactured by Microcraft Co., Ltd.). It was applied on the copper surface of registered trademark) M (manufactured by Nittetsu Chemical & Materials Co., Ltd.). Then, a cured film having a thickness of 20 μm was formed according to the above “(2) Conditions for forming a cured film”. Next, the obtained cured film was exposed to the obtained cured film under the conditions of a temperature of 85 ° C. and a humidity of 85% for 500 hours, left at room temperature for 24 hours, and then subjected to a cross-cut tape peel test using each of the prepared test substrates. This was carried out, and the number of remaining grids was counted out of 100 and evaluated based on the following criteria.

⊚: 100 ◯: 80 or more and 99 or less ×: 79 or less

As shown in Table 2, Examples 1 to 8 according to the present invention have adhesion, low warpage, and flexibility between the cured film (cured product) and the conductor circuit. Further, the flame retardancy could be improved by containing a compound having (E1) an aromatic ring and having two or more (meth) acryloyl groups, or by containing a phosphorus-based flame retardant. (See Examples 1 to 8). Further, by adding an ion scavenger, the adhesion between the cured film (cured product) and the conductor circuit was further improved (see Examples 6 and 7).

Claims (10)

1. (A) Equation (1)
   

   

   (In the formula (1), R ¹ may be linear, branched or cyclic, and represents a hydrocarbon group having 1 or more and 4 or less carbon atoms which may contain an ether bond (provided that the hydrocarbon group has 1 or more and 4 or less carbon atoms). It may have a substituent in the hydrocarbon group))
   With the polymerizable monomer represented by
   (B) A compound selected from the group consisting of melamine and its derivatives, and
   (C) Photopolymerization initiator and
   (D) Thermosetting component and
   A curable composition comprising.
2. The curable composition according to claim 1, which has a viscosity of 50 mPa · s or less at 50 ° C.
3. (E) The curable composition according to claim 1 or 2, which contains a compound having two or more (meth) acryloyl groups.
4. (E) The curing according to claim 3, wherein the compound having two or more (meth) acryloyl groups includes a compound having (E1) an aromatic ring and two or more (meth) acryloyl groups. Sex composition.
5. (D) The curable composition according to any one of claims 1 to 4, wherein the thermosetting component contains a latent thermosetting component.
6. The curable composition according to claim 5, wherein the latent thermosetting component is a blocked isocyanate compound.
7. (F) The curable composition according to any one of claims 1 to 6, further comprising a phosphorus-based flame retardant.
8. (G) The curable composition according to any one of claims 1 to 7, further comprising an ion scavenger.
9. A cured product obtained from the curable composition according to any one of claims 1 to 8.
10. An electronic component having the cured product according to claim 9.

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