KR20220161281A - Curable compositions, cured products and electronic components - Google Patents

Abstract

[Problem] To provide a curable composition having AMA ester, which has both adhesion to a conductor circuit, low warpage and flexibility, a cured product thereof, and an electronic component containing the cured product.
[Solution] (A) Formula (1) (in Formula (1), R ¹ may be straight-chain, branched-chain, or cyclic, and is a hydrocarbon having 1 to 4 carbon atoms which may contain an ether bond) A polymerizable monomer represented by a group (provided that the hydrocarbon group may have a substituent), (B) a compound selected from the group consisting of melamine and derivatives thereof, (C) a photopolymerization initiator, and (D) It is a curable composition containing a thermosetting component. As a result, the obtained cured product has high adhesion to the conductor circuit of the cured product, low warpage and flexibility.

Description

Curable compositions, cured products and electronic components

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

α-allyloxymethylacryloyl group-containing esters (hereinafter also referred to as AMA esters) are polymerized while cyclizing to form a main chain skeleton having as a repeating unit a 5-membered ring ether structure in which methylene groups are disposed on both sides. A cured product having has characteristics such as excellent thermal decomposition resistance, adhesion to a resin substrate, and tough mechanical properties.

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

Japanese Unexamined Patent Publication No. 2014-040585

As an insulating material for printed wiring boards, curable compositions applied on circuit boards are known, and these curable compositions are adjusted to various viscosities depending on the coating method.

However, a curable composition for use in printed wiring boards requires firm adhesion to conductor circuits, low warpage, and flexibility, and Patent Document 1 does not disclose these characteristics at all.

The inventors of the present invention found that the cured product described in Patent Literature 1 did not sufficiently have characteristics such as adhesion to a conductor circuit, low warpage, and flexibility required for use in an insulating material for a printed wiring board.

In view of the above problems, an object of the present invention is to provide, in a curable composition having AMA ester, a curable composition having both adhesion to a conductor circuit, low warpage and flexibility, a cured product thereof, and an electronic component containing the cured product. is to provide

The inventors of the present invention conducted intensive studies with the aim of achieving the above object. As a result, in addition to the α-allyloxymethyl acrylate ester compound and the photopolymerization initiator, a compound selected from the group consisting of melamine and derivatives thereof and a thermosetting component are blended into the curable composition, resulting in high adhesion to the conductor circuit of the obtained cured product; It was discovered that low warpage and flexibility could be realized, and the present invention was completed.

That is, the above object of the present invention is,

(A) Equation (1)

(In Formula (1), R ¹ may be straight-chain, branched-chain, 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 a substituent is selected from the hydrocarbon group) may have))

A polymerizable monomer represented by

(B) a compound selected from the group consisting of melamine and derivatives thereof;

(C) a photopolymerization initiator;

(D) heat curing component

It has been found that this is achieved by 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 (E) a compound having two or more (meth)acryloyl groups, (E) a compound having two or more (meth)acryloyl groups, (E1 ) It is more preferable to include a compound having an aromatic ring and two or more (meth)acryloyl groups.

Moreover, (D) It is preferable that the thermosetting component contains a latent thermosetting component, and it is more preferable that the latent thermosetting component is a block isocyanate compound.

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

Moreover, it is preferable that the curable composition of this invention further contains (G) an ion trapping agent.

Moreover, the said object of this invention can be achieved also by the hardened|cured material obtained from the curable composition of this invention, and the electronic component which has this hardened|cured material.

According to the curable composition of the present invention, the obtained cured product has both high adhesion to the conductor circuit, low warpage and flexibility. Also, the cured product obtained from the curable resin composition of the present invention and the electronic component having the cured product each have similarly high adhesion to the conductor circuit, low warpage, and flexibility.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the MIT test performed with respect to the cured film obtained from a curable composition.

<Curable composition>

The curable composition of the present invention,

(A) Equation (1)

(In Formula (1), R ¹ may be straight-chain, branched-chain, 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 a substituent is selected from the hydrocarbon group) may have))

A polymerizable monomer represented by (hereinafter also referred to as a polymerizable monomer of formula (1) in (A));

(B) a compound selected from the group consisting of melamine and derivatives thereof;

(C) a photopolymerization initiator;

(D) heat curing component

have

[(A) polymerizable monomer of formula (1)]

The polymerizable monomer of (A) formula (1) contained in the curable composition of the present invention can suppress warpage of the cured product after exposure, particularly on a flexible printed wiring board having flexibility. When the curvature of the cured product becomes large, the entire flexible printed wiring board becomes cylindrical, and a problem arises in that the curable composition cannot be applied to an appropriate position when applying by sweeping. Moreover, in the case of inkjet printing use, the problem of coming into contact with an inkjet head arises when a flexible printed wiring board is bent. And there also existed a problem that warpage became larger at the time of thermosetting. However, in the curable composition of the present invention, since the polymerizable monomer of (A) Formula (1) is contained, warpage of the cured product after exposure can be suppressed, and furthermore, warpage after thermal curing can also be suppressed.

The polymerizable monomer of (A) formula (1) contained in the curable composition of the present invention is, for example, the following formula a):

(In formula (a), R ¹ is the same as R ¹ in formula (1), and X· represents an initiation radical or a growth radical.) Since the polymerization reaction proceeds while cyclization, methylene groups are placed on both sides It is thought to form a main chain skeleton having one 5-membered ring ether structure as a repeating unit.

As said hydrocarbon group of 1 or more and 4 or less carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, vinyl group, allyl group, A methallyl group, a crotyl group, a cyclopropyl group, a cyclobutyl group, a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an ethoxyethyl group, a vinyloxyethyl group, etc. are mentioned.

As said substituent, For example, chain|strand-shaped unsaturated hydrocarbon groups, such as a vinyl group, an allyl group, a methallyl group, and a crotyl group; Alkoxy groups, such as a methoxy group, an ethoxy group, and a methoxy ethoxy group; Alkylthio groups, such as a methylthio group and an ethylthio group; Acyl groups, such as an acetyl group and a propionyl group; Acyloxy groups, such as an acetyloxy group and a propionyloxy group; Alkoxycarbonyl groups, such as a methoxycarbonyl group and an ethoxycarbonyl group; Alkylthiocarbonyl groups, such as a methylthiocarbonyl group and an ethylthiocarbonyl group; Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Urei Dogi; amide group; cyano group; A trimethylsilyl group etc. are mentioned.

R ¹ is (A) 1 carbon number from the viewpoint of industrial production ease of the polymerizable monomer of the formula (1) and (A) lowering the viscosity of the polymerizable monomer of the formula (1) to reduce the viscosity of the curable composition A chain saturated hydrocarbon group of 1 to 4 carbon atoms, a chain unsaturated hydrocarbon group of 1 to 4 carbon atoms and a hydrocarbon group having 1 to 4 carbon atoms and an ether bond are preferred, and methyl, ethyl, n-propyl, An isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, allyl group, methallyl group, crotyl group, methoxyethyl group, ethoxyethyl group and vinyloxyethyl group are more preferred.

(A) As a polymerizable monomer of Formula (1), for example, α-allyloxymethyl methyl acrylate, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl n-propyl acrylate, α-allyloxymethyl acrylate isopropyl , α-allyloxymethyl n-butyl acrylate, α-allyloxymethyl sec-butyl acrylate, α-allyloxymethyl tert-butyl acrylate, α-allyloxymethyl vinyl acrylate, α-allyloxymethyl allyl acrylate, α-allyl methyl oxymethyl acrylate, α-allyloxymethyl crotyl acrylate, α-allyloxymethyl methoxymethyl acrylate, α-allyloxymethyl methoxyethyl acrylate, α-allyloxymethyl methoxypropyl acrylate, α-allyloxymethyl methoxybutyl acrylate, α-allyloxymethyl ethoxymethyl acrylate, α-allyloxymethyl ethoxyethyl acrylate, α-allyloxymethyl vinyloxyethyl acrylate, and the like. These may be used independently, respectively, and may use two or more types together.

(A) The polymerizable monomer of formula (1) can be adjusted according to the method described in Unexamined-Japanese-Patent No. 2014-040585, Unexamined-Japanese-Patent No. 2011-137123 etc., for example.

(A) The compounding amount of the polymerizable monomer of formula (1) is preferably 1 part by mass or more and 80 parts by mass or less, more preferably 5 parts by mass or more and 60 parts by mass or less, based on 100 parts by mass of the curable composition of the present invention. , Particularly preferably, they are 5 parts by mass or more and 50 parts by mass or less.

[(B) a compound selected from the group consisting of melamine and its derivatives]

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

(B) Examples of the compound selected from the group consisting of melamine and derivatives thereof include guanamines such as acetoguanamine and benzoguanamine; melamine; and triazine derivatives such as ethyldiamino-S-triazine, 2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine. It is preferably melamine.

(B) The compound selected from the group which consists of melamine and its derivative(s) can be used individually by 1 type or in mixture of 2 or more types. (B) When a compound selected from the group consisting of melamine and its derivatives is blended into the curable composition of the present invention, the blending amount is, when the total amount of the thermosetting component (D) described later is 100% by mass, preferably It is 0.1 mass % or more and 20 mass % or less, More preferably, it is 0.5 mass % or more and 20 mass % or less, Especially preferably, it is 1 mass % or more and 15 mass % or less.

(B) The storage stability of the curable composition is improved by setting the compounding amount of the compound selected from the group consisting of melamine and derivatives thereof to 0.1% by mass or more and 20% by mass or less when the total amount of the (D) thermosetting component is 100% by mass. Favorable thermal curing can be realized while increasing.

[(C) Photopolymerization Initiator]

(C) As the photopolymerization initiator, any compound can be used as long as it generates radicals by light, laser, electron beam or the like and initiates a radical polymerization reaction. 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; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1 aminoacetophenones such as -one and N,N-dimethylaminoacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 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, and 2-mercaptobenzothiazole; organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, and tribromomethylphenylsulfone; benzophenones or xanthones such as benzophenone and 4,4'-bisdiethylaminobenzophenone; acyl phosphines such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carb oxime esters such as bazol-3-yl]- and 1-(O-acetyl oxime); and the like.

Said (C) photoinitiator can be used individually by 1 type or in mixture of 2 or more types. 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. of photoinitiation aids can be used. In addition, a titanocene compound such as Omnirad 784 (manufactured by IGM Resins B.V.), which has absorption in the visible light region, may also be added to (C) the photopolymerization initiator in order to promote the photoreaction. In addition, the component added to the photopolymerization initiator is not limited to these, and absorbs light in the ultraviolet or visible light region and radically polymerizes an ethylenically unsaturated group such as a (meth)acryloyl group. It is not limited to, It can use individually or in combination of multiple.

(C) As a product name of what is marketed as a photoinitiator, Omnirad 907, Omnirad 127, Omnirad 379EG (all are made by IGM Resins B.V.) etc. are mentioned, for example.

Further, (C) the photopolymerization initiator may be a compound that initiates a cationic polymerization reaction. Examples of such (C) photopolymerization initiator include diphenyliodonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, and commercially available products. As such, sulfonium salt-based photocationic polymerization initiators such as Optoma-SP-170 and SP-152 manufactured by ADEKA Co., Ltd., CPI-100P, CPI-101A, CPI-200K, and CPI-210S manufactured by San-Apro Co., Ltd., and IR manufactured by BASF Co., Ltd. Gacure (registered trademark) 261 etc. are mentioned.

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

[(D) Heat Curing Component]

Moreover, the curable composition of this invention contains (D) thermosetting component. (D) The thermosetting component is different from the polymerizable monomer of (A) Formula (1), and (D) by including the thermosetting component, in addition to improving the adhesion of the cured film to the conductor circuit, heat resistance and plating resistance , flexibility, solvent resistance, flame retardancy, etc. can be further improved.

(D) As a thermosetting component, well-known compounds, such as a block isocyanate compound, an epoxy compound, and an oxetane compound, can be used, for example.

Among them, in the present invention, a latent thermosetting component in which a functional group in the structure is protected by a protecting group can be preferably used. By using such a latent thermosetting component, unintended reactions in the curable composition under unexpected conditions can be suppressed, and storage stability of the curable composition can be improved. In addition, such a curable composition is excellent in inkjet printability at 50°C, and when cured, it can be easily deprotected by heating or the like, so that latent thermosetting components can be activated. In the present invention, latent means a property that exhibits thermosetting properties by being activated by heating at a high temperature of 80 ° C. or higher, although it does not show activity at room temperature or slightly warmed conditions.

It is preferable that this latent thermosetting component is a block isocyanate compound. A block isocyanate compound is a compound which preferably has a plurality of blocked isocyanate groups in one molecule. A blocked isocyanate group is a group in which an isocyanate group is protected and temporarily inactivated by a reaction with a blocking agent, and when heated to a predetermined temperature, the blocking agent dissociates to generate an isocyanate group.

As a polyisocyanate compound which has a some isocyanate group, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is used, for example.

Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, and o-xylyl. Rendiisocyanate, m-xylylenediisocyanate, 2,4-tolylene dimer, etc. are mentioned.

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

As a specific example of alicyclic polyisocyanate, bicycloheptane triisocyanate is mentioned. And the adduct form of the isocyanate compound exemplified above, the biuret form, the isocyanurate form, etc. are mentioned.

Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; active methylene-based 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, glycol alcohol-based blocking agents such as butyl acid, diacetone alcohol, methyl lactate and ethyl lactate; oxime-based blocking agents such as formaldehyde, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide-based blocking agents such as succinic acid imide and maleic acid imide; amine blocking agents such as xylidine, aniline, butylamine, and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine; Pyrazole type blocking agents, such as dimethyl pyrazole, etc. are mentioned.

The block isocyanate compound may be a commercially available one, for example, duranate TPA-B80E, 17B-60PX, E402-B80T (all manufactured by Asahi Kasei Co., Ltd.), TrixeneBI7982: block isocyanate (hexamethylene isocyanate (HDM) trimer, blocking agent : Dimethylpyrazole (DMP), manufactured by Baxenden Chemicals), etc. are mentioned.

Moreover, as a latent thermosetting component, 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, or a carboxyl group-containing compound may be used.

(D) The blending amount of the thermosetting component 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) Functionalities such as heat resistance and plating resistance of a cured film while maintaining storage stability of the curable composition of the present invention by the compounding amount of the thermosetting component being 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. can be further improved.

[(E) A compound having two or more (meth)acryloyl groups]

It is preferable that the curable composition of this invention contains the compound which has 2 or more (E) (meth)acryloyl groups. (E) A compound having two or more (meth)acryloyl groups is a component blended in order to be cured by a photopolymerization reaction and to form a cured product. In addition, the compound which has two or more (E) (meth)acryloyl groups is different from the polymerizable monomer of (A) Formula (1).

By having 2 or more (meth)acryloyl groups, favorable sclerosis|hardenability by a photopolymerization reaction can be obtained. Here, a (meth)acryloyl group is a general term for an acryloyl group and a methacryloyl group.

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

(E1) Examples of the compound having an aromatic ring and two or more (meth)acryloyl groups include (meth)acrylates of polyhydric phenols and alkylene oxide adducts thereof.

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

As an alkylene oxide, ethylene oxide, a propylene oxide, and a butylene oxide are mentioned, for example. It is preferable that the addition number of alkylene oxide is 6 or less.

(E1) As a commercial item of the compound which has an aromatic ring and has two or more (meth)acryloyl groups, ABE-300 (made by Shin-Nakamura Chemical Industry Co., Ltd.), BPE-80N (made by Shin-Nakamura Chemical Industry Co., Ltd.), BPE- 100 (made by Shin-Nakamura Gagaku High School), A-BPE-4 (made by Shin-Nakamura Gagaku High School), BPE-4 (made by Daiichi High School Seiyaku Co., Ltd.), BPE-10 (made by Daiichi High School Seiyaku Co., Ltd.) Kaisha), BPE-200 (made by Shin Nakamura Chemical Industry Co., Ltd.), EBECRYL 150 (made by Daicel Allnex Co., Ltd.), etc. are mentioned.

Further, (E) The compound having two or more (meth)acryloyl groups includes a compound having two or more low-viscosity (meth)acryloyl groups from the viewpoint of obtaining good curability while reducing the viscosity of the curable composition. it is desirable Here, (E) The compound which has two or more (meth)acryloyl groups WHEREIN: Low viscosity means that the viscosity in 50 degreeC is 50 mPa*s or less, especially the viscosity in 50 degreeC is 20 mPa*s or less.

Examples of the compound having two low-viscosity (meth)acryloyl groups include bifunctional (meth)acryloyl group-containing monomers that are esters of alkylene glycol and (meth)acrylic acid.

Alkylene glycol may be monoalkylene glycol or may have 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.

Diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, tripropylene glycol, tributylene glycol, etc. are mentioned as what has a repeating structure of 2 or more alkylene glycol.

Specifically, examples of the compound having two low-viscosity (meth)acryloyl groups include diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and dibutylene glycol di(meth)acrylate. , triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tributylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4- Butanedioldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1,9-nonanediol acrylate, 1,10-decanedioldiacrylate, 1,16-hexadecanedioldiacrylate etc. can be mentioned.

Commercially available 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 Allnex Co.), and T0948 (Tokyo Kasei Kogyo Co., Ltd.), T2389 (Tokyo Kasei Kogyo Co., Ltd.), Biscott #310HP (Osaka Yuki Kagaku Kogyo Co., Ltd.), PE-200 (Daiichi Kogyo Seiyaku Co., Ltd.), PE-300 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), HDDA (manufactured by Daicell Allnex), L-C9A (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), A-NOD-N (Shin Nakamura Kagaku Kogyo) manufactured), B1065 (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 1,9-NDA (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

Moreover, in order to further improve the curability by photopolymerization reaction, it is preferable that (E) the compound which has 2 or more (meth)acryloyl groups contains the compound which has 3 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 epichloro. Hydrin-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, tetramethylolmethane tetraacrylate, ethylene oxide-modified phosphoric acid triacrylate, propylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate , dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, or polyfunctional acrylates represented by silsesquioxane-modified products thereof, or methacrylate monomers corresponding to these, ε caprolactone-modified tris An acryloxyethyl isocyanurate is mentioned.

In addition, a multi-branched oligomer or polymer may be sufficient as the compound which has 3 or more (meth)acryloyl groups.

(E) The compound having two or more (meth)acryloyl groups is preferably 10 parts by mass or more and 90 parts by mass or less, 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. , Particularly preferably, they are 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, it is uniformly dispersed, and good coating properties are obtained. When it is below parts by mass, the effect of improving heat resistance is obtained.

[(F) phosphorus flame retardant]

It is preferable that the curable composition of this invention contains the well-known and usual (F) phosphorus flame retardant for the purpose of improving the flame retardance of the hardened|cured material obtained.

(F) Examples of the phosphorus-based flame retardant include phosphoric acid esters and condensed phosphoric acid esters, phosphorus-containing compounds having phenolic hydroxyl groups, phosphazene compounds, phosphinic acid metal salts, and the following general formula (2)

(In 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 to 4 carbon atoms, and R ⁴ is a hydrogen atom or 1 carbon atom which may be substituted with a cyano group. It is preferably an alkyl group of at least four but not more than four, a 2,5-dihydroxyphenyl group, or a 3,5-di-t-butyl-4-hydroxyphenyl group, but is not limited thereto.

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

Examples of the phosphorus-containing compound having a phenolic hydroxyl group include those in which R ⁴ is a phenyl group substituted with a hydroxyl group in the general formula (2). As a commercial item, there exist HCA-HQ by Sanko Corporation etc.

As a phosphinic acid metal salt, for example, the following structural formula (3)

(In formula (3),

R ₁ and R ₂ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 12 or less carbon atoms;

M represents calcium, aluminum or zinc, when M represents aluminum, m = 3, and when representing other metals, m = 2)

It is preferable to have a structure represented by

More preferably, it is a compound which has a structure in which M represents aluminum in Formula (3).

By using a phosphinic acid metal salt, flame retardancy can be improved without impairing the flexibility of a 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-1,4 -(dimethylphosphinic acid), methylphenylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, and mixtures thereof.

As a commercial item, Exolit OP 1240, 1240, 1312, 1400, 930, 945TP, and OP-935 are mentioned, for example.

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

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

In another preferred embodiment, both phenoxy groups bonded to the phosphorus atom in the hexaphenoxycyclotriphosphazene structure are substituted with one cyano group (-CN), and the phenoxy group thus substituted is hexaphenoxy It is a structure having all six cyclotriphosphazene structures as a whole.

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

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

or

or

It has the structure of any of them.

As a commercial item of a preferable phosphazene compound, FP-300B, FP-300, and SPH-100 (all are made by Fushimi Pharmaceutical Co., Ltd.) are mentioned, for example.

(F) Phosphorus flame retardant may be used individually by 1 type, and may use 2 or more types together. (F) When a phosphorus-based flame retardant 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 or more and 40 parts by mass or less with respect to 100 parts by mass of the curable composition of the present invention. In particular, the compounding amount of the phosphorus-based flame retardant (F) is preferably 0.1 to 10%, more preferably 1 to 5%, in terms of the phosphorus content in the curable composition of the present invention. (F) When the phosphorus-based flame retardant is blended within the above range, flame retardancy can be effectively imparted while maintaining heat resistance and low warpage. In addition, in the curable composition of the present invention, you may use borate metal salts (zinc borate compound (2ZnO*3B ₂ O ₃ *3.5H ₂ O)), such as Firebrake ZB, as a flame retardant.

[(G) ion trapping agent]

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

(G) As the ion trapping agent, an inorganic cation trapping agent that captures cations by ion exchange, an inorganic anion trapping agent that captures anions by ion exchange, and an inorganic zwitterion that captures both cations and anions by ion exchange A trapping agent can be mentioned, and an inorganic zwitterion trapping agent is preferable.

(G) The ion trapping agent contains at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, and bismuth. In particular, two or more types of oxidized hydrates or hydroxides of these components are preferable, and two or more types of oxidized hydrates or hydroxides selected from the group consisting of zirconium, magnesium, and aluminum are more preferable. Among them, hydrotalcite, which is a three-component oxide hydrate of magnesium, aluminum and zirconium, a two-component oxide hydrate of bismuth and zirconium, and a hydroxide containing magnesium and aluminum, is preferable. An ion trapping agent may be used individually by 1 type, and may be used in combination of 2 or more types.

Hydrotalcite is represented by the following formula (1).

Mg _a Al _b (OH) _c (CO ₃ ) _d ㆍnH ₂ O . (One)

(In formula (1), a, b, c, and d are positive numbers and satisfy 2a+3b-c-2d=0. In addition, n represents the number of hydration numbers and is 0 or a positive number, preferably 1 to 5.)

In Formula (1), those in which a part of Mg is substituted with other divalent metal ions can also be preferably used in the same way. Among other divalent metal ions, Zn is particularly preferred.

Specific examples of the hydrotalcite 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 ㆍnH ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃ ㆍnH ₂ O, Mg _4.3 Al ₂ (OH) _12.6 CO ₃ ㆍnH ₂ O, Mg _2.5 Zn ₂ Al ₂ (OH) ₁₃ CO ₃ ㆍnH ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃ ㆍnH ₂ O, Mg _4.2 Al ₂ (OH) _12.4 CO ₃ ㆍnH ₂ O, Mg ₄ Al ₂ (OH) ₁₂ CO ₃ ㆍnH ₂ O (above, n represents the number of hydration and is 0 or a positive number, preferably 1 to 5.), among which Mg _4.3 Al ₂ (OH) _12.6 CO ₃ nH ₂ O is preferable. .

As the hydrotalcite represented by 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 still more preferably 1.8 or more and 2.5 or less.

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

In addition, the average particle diameter of the ion trapping agent can be measured by a dynamic light scattering method. Specifically, it can be measured by creating a particle size distribution of the ion trapping agent on a volume basis with a dynamic light scattering type particle size distribution analyzer and taking the median diameter (D50) as the average particle diameter. As the measurement sample, a sample obtained by dispersing an ion trapping agent in water by ultrasonic waves can be preferably used. As a dynamic light scattering type particle size distribution measuring device, Nanotrac Wave II UT151 manufactured by Microtrac Bell, etc. can be used.

(G) Commercially available products may be used as the ion trapping agent, for example, DHT- by Kyowa Chemical Industry Co., Ltd. 4A, DHT-4A-2, DHT-4C, etc. are mentioned.

(G) When an ion trapping agent is blended, the blending amount is preferably 0.01 part by mass or more and 10 parts by mass or less, more preferably 0.02 part by mass or more and 5 parts by mass, based on 100 parts by mass of the curable composition of the present invention. or less, more preferably 0.03 parts by mass or more and 3 parts by mass or less. When the compounding amount of the ion trapping agent is within the above numerical range, it is possible to improve insulation reliability and adhesion after high temperature and high humidity without deteriorating flexibility, low warpage, and flame retardancy.

[Compounds having (meth)acryloyl groups and hydroxyl groups ((E) excluding compounds having two or more (meth)acryloyl groups)]

Moreover, it is preferable that the curable composition of this invention contains the compound which has a (meth)acryloyl group and a hydroxyl group. By including the compound having a (meth)acryloyl group and a hydroxyl group, the adhesiveness between the obtained cured film, conductor and substrate is improved.

As a compound having a (meth)acryloyl group and 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, and the like. As commercially available products, Aronix M-5700 (trade name manufactured by Toagosei Co., Ltd.), 4HBA, 2HEA, CHDMMA (above, trade name manufactured by Kyoeisha Chemical Co., Ltd.), BHEA, HPA, HEMA, HPMA (above, trade name manufactured by Nippon Shokubai Co., Ltd.) ), light ester HO, light ester HOP, light ester HOA (above, the trade name of Kyoeisha Chemical Co., Ltd.) and the like. The compound which has a (meth)acryloyl group and a hydroxyl group can be used combining 1 type or multiple types.

Among these, especially 2-hydroxy-3-acryloyloxypropyl acrylate, 2-hydroxy-3-phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4- Hydroxybutyl acrylate and 1,4-cyclohexanedimethanol monoacrylate are preferably used. Moreover, from a viewpoint of the ease of viscosity adjustment, the compound with one (meth)acryloyl group is used preferably.

The compounding 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 preferably 2 parts by mass per 100 parts by mass of the curable composition of the present invention. to 8 parts by mass.

The curable composition of the present invention may contain additives such as antioxidants, antifoaming/leveling agents, thixotropy imparting agents/thickeners, coupling agents, dispersing agents, polymerization retardants, and colorants as needed.

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

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 it has a viscosity which can be jetted 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 particularly preferably 15 mPa·s or less at 50°C. Viscosity was measured at 50°C, 100 rpm, and 30 seconds according to the viscosity measurement method using a 10-cone-flat rotational viscometer of JIS Z8803:2011, and a cone plate viscometer (TVE) using 1°34'×R24 as a cone rotor. -33H, manufactured by Toki Sangyo Co., Ltd.).

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

In addition, 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 used for printing onto a substrate.

<Cured product obtained from curable composition>

The hardened|cured material obtained by the curable composition of this invention is obtained by photocuring the composition layer, for example by irradiating an active energy ray of 50 mJ/cm<2> - 1000 mJ/cm<2> to the composition layer immediately after the said printing. Active energy ray irradiation is performed by irradiation with active energy rays such as ultraviolet rays, electron beams, and actinic rays, preferably by ultraviolet rays.

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

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 heating conditions, it is preferable to heat at 130°C to 170°C for 5 minutes to 90 minutes.

Since the hardened|cured material obtained by the curable composition of this invention is also excellent in a softness|flexibility, it is especially suitable also as a soldering resist with respect to a flexible printed wiring board.

As a board|substrate of a flexible printed wiring board, the film etc. which consist of glass polyimide, a polyimide, a polyethylene terephthalate, a liquid crystal polymer, polycarbonate etc. are mentioned, for example.

<Electronic component having cured product of curable composition>

In this way, when a cured film containing a curable composition pattern-printed on a substrate is used as a solder resist, it is heated in a soldering process for mounting components. Soldering may be performed by hand soldering, flow soldering, reflow soldering, and the like, but in the case of reflow soldering, for example, preheating at 100°C to 140°C for 1 to 4 hours, followed by 240°C to 280°C Heating for about 5 to 20 seconds is repeated a plurality of times (for example, 2 to 4 times) to provide a reflow process in which the solder is heated and melted, and after cooling, an electronic component with components mounted as necessary is completed. .

Further, in the present invention, electronic components refer to components used in electronic circuits, and other active components such as printed wiring boards, transistors, light emitting diodes, laser diodes, resistors, capacitors, inductors, and passive components such as connectors are also included. , The cured products of the curable composition of the present invention exhibit 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 applicability, and has little warpage after photocuring. In addition, since it is flexible even after curing and has excellent adhesion to substrates, flame retardancy, solder heat resistance, plating resistance, and solvent resistance, it can be applied to various applications, and the application target is not particularly limited. For example, it can be used for the production of etching resists, solder resists, and marking inks for printed wiring boards using an inkjet method, and among them, it can be suitably used as a solder resist for flexible printed wiring boards requiring high heat resistance and flexibility.

In addition, it can be used for applications such as materials for UV molded articles, materials for stereolithography, and materials for 3D inkjet.

In addition, the present invention is not limited to the configurations and examples of the above embodiments, and various modifications are possible within the scope of the gist of the invention.

Example

Hereinafter, the present invention will be described in detail by showing examples, but the present invention is not limited only to these examples. In addition, unless otherwise indicated below, "part" shall mean a mass part.

<1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3>

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

*1: α-(allyloxymethyl)methyl 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 Daiichi Kogyo Seiyaku Co., Ltd.)

*4: Dipropylene glycol diacrylate (DPGDA: manufactured by Toyo Chemicals)

*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 block 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 Seiyakusho Co., Ltd.)

*11: Phosphinic acid metal 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 trapping agent 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 Yellow 147)

<2. evaluation>

Above <1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> The viscosity of each curable composition obtained was evaluated as follows. In addition, test samples were prepared as shown below, and applicability, post-exposure warpage, flexibility (MIT test), solder heat resistance, solvent resistance, electroless gold plating resistance, flame retardancy, and adhesion after high temperature and high humidity were evaluated. The results are shown in Table 2.

(1) Viscosity

Above <1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> For each curable composition obtained, a value of 50 ° C., 100 rpm, 30 seconds, and a cone plate type viscometer using 1 ° 34 'x R24 as a cone rotor (TVE-33H, manufactured by Toki Sangyo Co., Ltd.), and evaluated according to the following criteria.

◎: 10 mPa·s or less

○: More than 10 mPa·s and 20 mPa·s or less

×: Exceeding 20 mPa·s

(2) Conditions for forming a cured film

Above <1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each of the curable compositions obtained was applied using an inkjet printing device CPS6151 (manufactured by Microcraft). As the array, KM1024iSHE (manufactured by Konica Minolta Co., Ltd., coating droplet amount 6pL, 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. Thereafter, the heating device performed main curing at 150°C for 60 minutes using a hot air circulation drying furnace DF610 (manufactured by Yamato Chemical Co., Ltd.).

(3) Applicability

Above <1. [Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3] Spanex (registered trademark) M (Nippon) after sulfuric acid treatment of each curable composition obtained by using an inkjet printing device CPS6151 (manufactured by Microcraft) Tetsu Chemical & Materials Co., Ltd.) was coated on a copper surface with a coating thickness of 20 μm. The surface of the cured film was visually observed and evaluated according to the following criteria.

○: uniformly applied and smooth surface

△: The entire surface is coated, but streaks are generated in the direction of head operation

x: What omission occurred in a part of the cured film

(4) Flexibility after exposure

Above <1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained by using an inkjet printing device CPS6151 (manufactured by Microcraft) was subjected to sulfuric acid treatment under photocuring conditions of 800 mJ/cm 2 Kapton (Registered trademark) 200H (manufactured by DuPont Toray) was applied on one side. The obtained laminated body of the post-exposure cured film was cut into 5 cm x 5 cm (length x width) to make a sample (film thickness: 15 µm). Each sample was allowed to stand on a horizontal workbench for 30 minutes with the cured film surface as the upper surface after exposure, and the height of the four steps of the sample raised from the workbench was regularly measured, and the average value of the four steps was obtained. The same test was performed three times for each sample, the average value of the three tests was obtained, and the following criteria were evaluated.

◎: The average value of the total height of the 4 stages is 5 mm or less

○: The average value of the total height of the 4 stages is more than 5 mm and less than 10 mm

×: The average value of the total height of the 4 stages 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> Each curable composition obtained by Microcraft CP56151 was prepared by sulfuric acid-treated copper with a thickness of 12 μm and a circuit pattern formed of 25 μm of polyimide. applied on a substrate. Thereafter, 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 an MIT test (R = 0.38 mm) based on JIS P8115 to evaluate flexibility.

Specifically, as shown in FIG. 1, the test piece 1 is attached to the apparatus, and in a state where a load F (0.5 kgf) is applied, the test piece 1 is vertically installed on the clamp 2 and bent. The bending was performed at an angle α of 135 degrees and a speed of 175 cpm, and the number of reciprocal bending until breakage (times) was measured. In addition, the test environment was 25 degreeC, and the radius of curvature was set to R=0.38 mm. The evaluation criteria are as follows.

◎: 150 times or more

○: 100 to 149 times

△: 50 to 99 times

×: 49 times or less

(6) Solder heat resistance

Above <1. Preparation of the Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained by using an inkjet printing device CPS6151 (manufactured by Microcraft) was subjected to sulfuric acid treatment under photocuring conditions of 800 mJ / cm 2 Copper Coating was performed on a circuit pattern substrate having a thickness of 12 μm and a polyimide of 50 μm. Thereafter, 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 was applied to the obtained evaluation substrate, and immersion was performed once or twice for 5 seconds in a soldering bath set at 260° C. in advance, and the flux was washed with denatured alcohol, followed by a cross-cut tape peeling test. Expansion and peeling were evaluated. The criterion for judgment is as follows.

(double-circle): Peeling is not recognized by a cured film even if it is immersed for 5 seconds x 2 times and a peel test is performed with cellophane tape (registered trademark).

O: Peeling is not recognized by a cured film even if it is immersed for 5 seconds x 1 time and a peel test is performed with cellophane tape (registered trademark).

x: When dipping for 5 seconds x 1 time, the cured film has swelling and peeling.

(7) Solvent resistance

Above <1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained by using an inkjet printing device CPS6151 (manufactured by Microcraft) was subjected to sulfuric acid treatment under photocuring conditions of 800 mJ / cm 2 Espa The coating was applied on the copper surface of Nex (registered trademark) M (manufactured by Nittetsu Chemical & Materials Co., Ltd.) and heated at 150°C for 60 minutes in a hot air circulation type drying furnace to obtain a cured film having a thickness of 20 µm. The state of the cured film after immersing the cured film in propylene glycol monomethyl acetate for 30 minutes was evaluated. The evaluation criteria are as follows.

○: No change was observed at all

△: Very slightly changed

×: What is remarkably changed

(8) Resistance to electroless gold plating

Above <1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained by using an inkjet printing device CPS6151 (manufactured by Microcraft) was subjected to sulfuric acid treatment, copper thickness 12 μm, polyimide 50 μm was applied on a circuit pattern substrate of Thereafter, a cured film having a thickness of 20 μm was formed according to the above “(2) conditions for forming a cured film”. About the obtained evaluation board|substrate, gold plating was performed on conditions of 5 micrometers of nickel and 0.03 micrometer of gold using a commercially available electroless nickel plating bath and electroless gold plating bath, and the surface state of the cured film was observed. The evaluation criteria are as follows.

○: No change was observed at all

×: Significantly whitened or clouded

(9) Flame retardancy

Above <1. Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3> Each curable composition obtained by> was coated on both sides on a FR-4 (0.8 mmt) substrate using an inkjet printing device CPS6151 (manufactured by Microcraft). did Thereafter, a cured film was formed according to the above "(2) Conditions for forming a cured film" (the coating film thickness of each surface is 20 µm). The obtained cured film was subjected to a foil vertical burning test in accordance with the UL94 standard. The evaluation criteria are as follows.

◎: Passed V-0, and the burning time of each sample was less than 3 seconds

○: Passed V-0, and the burning time of each sample was more than 3 seconds and less than 7 seconds

V-0: Passing V-0, and the burning time of each sample exceeding 7 seconds and less than 10 seconds

Not: V-0 disqualified

(10) Adhesion after high temperature and high humidity

Above <1. [Preparation of Curable Compositions of Examples 1 to 8 and Comparative Examples 1 to 3] Spanex (registered trademark) M (Nippon) after sulfuric acid treatment of each curable composition obtained by using an inkjet printing device CPS6151 (manufactured by Microcraft) Coating was performed on the copper surface of Tetsu Chemical & Materials Co., Ltd.). Thereafter, 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 for 500 hours under the conditions of a temperature of 85 ° C. and a humidity of 85%, and then left at room temperature for 24 hours. Then, a cross-cut tape peeling test was conducted using each test board produced. , How many of the remaining number of checkerboard eyes were counted out of 100, and evaluated based on the following criteria.

◎: 100 pieces

○: 80 or more and 99 or less

×: 79 or less

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

Claims (10)

(A) Equation (1)

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

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