WO2021200258A1 - Curable composition, cured product, and printed wiring board - Google Patents

Abstract

[Problem] Provided is a curable composition having excellent flexibility and resolution and excellent adhesion to copper. [Solution] A curable composition according to the present invention is characterized by including: (A) an ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony, and bismuth; (B) a photosensitive monomer; and (C) a photopolymerization initiator.

Description

Curable composition, cured product, and printed wiring board

The present invention relates to a curable composition. The present invention also relates to a cured product obtained by curing the curable composition and a printed wiring board including the cured product.

In recent years, attention has been focused on solder resist inks that can be printed by the inkjet method from the viewpoint of workability and environmental issues. It is not necessary to perform plate making as in the case of forming a resist pattern by the screen printing method, which saves time and effort, and can reduce the work man-hours by reducing the amount of developer, cleaning solution, and high molecular weight photosensitive resin used. ..

Japanese Unexamined Patent Publication No. 2016-147970 Japanese Unexamined Patent Publication No. 2012-92312 Japanese Unexamined Patent Publication No. 2012-87298

However, conventional curable compositions such as those used in Patent Documents 1 to 3 are particularly inferior in adhesion after being left in high temperature and high humidity conditions, and have a problem that it is difficult to secure reliability over a long period of time. rice field. As a result, when an attempt was made to draw a fine pattern, peeling or crushing of the pattern was observed, and the development of a curable composition having excellent both adhesion and resolution was eagerly desired.

Therefore, an object of the present invention is to provide a curable composition having excellent flexibility and resolution, and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions.

Another object of the present invention is to provide a cured product obtained by curing the composition and a printed wiring board provided with the cured product.

As a result of diligent studies, the present inventors have found that the oxidation of the copper surface on which the cured film of the curable composition is formed causes a decrease in adhesion. By blending a specific ion scavenger, a photosensitive monomer, and a photopolymerization initiator into the curable composition, the adhesion to copper after the accelerated test is excellent, which greatly affects the improvement in yield. I found that. In addition, the present inventors have surprisingly found that it is possible to provide a cured product having excellent flexibility and resolution in addition to the effect of improving the adhesion to copper, and the present invention has been made. Has been completed.

That is, the curable composition according to the present invention comprises (A) an ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth, and (B) photosensitive. It is characterized by containing a sex monomer and (C) a photopolymerization initiator.

In the aspect of the present invention, it is preferable that the curable composition further contains (D) a thermosetting component and contains a blocked isocyanate as a thermosetting component.

In the aspect of the present invention, the content of the ion scavenger is preferably 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the curable composition.

In the aspect of the present invention, it is preferable that the photosensitive monomer contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.

In the aspect of the present invention, the viscosity of the curable composition at 50 ° C. is preferably 50 mPa · s or less.

In the aspect of the present invention, it is preferable that the curable composition is for inkjet printing.

The cured product according to another aspect of the present invention is characterized by being a cured product obtained by curing the curable composition.

The printed wiring board according to another aspect of the present invention is characterized by being a printed wiring board provided with the cured product.

According to the present invention, it is possible to provide a curable composition having excellent flexibility and resolution, and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions. In particular, the curable composition according to the present invention is suitable for inkjet printing. Further, in another aspect of the present invention, it is possible to provide a cured product obtained by curing the composition and a printed wiring board provided with the cured product.

[Curable composition]
The curable composition according to the present invention comprises (A) an ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth, and (B) photosensitive. It contains a sex monomer and (C) a photopolymerization initiator. The curable composition according to the present invention preferably further contains (D) a thermosetting component. Hereinafter, each component constituting the curable composition according to the present invention will be described.

[(A) Ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth]
The ion scavenger contained in the curable composition according to the present invention includes an inorganic scavenger that captures cations by ion exchange, an inorganic anion scavenger that captures anions by ion exchange, and cations by ion exchange. Examples thereof include an inorganic amphoteric scavenger that traps both ions and anions, and an inorganic amphoteric scavenger is preferred. It is considered that this is because the influence on the flexibility can be reduced and the inkjet droplets can be stably ejected by blending the ion supplement material having a small particle size. Further, by adding the ion scavenger, the oxidation of the base material is suppressed, and the adhesion to copper can be further ensured.

The ion scavenger contained in the curable composition according to the present invention contains at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony 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 an ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth 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 a 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 (D ₅₀ ) 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" manufactured by Microtrac Bell can be used.

A commercially available ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth may be used, for example, "IXEPLAS-A1" manufactured by Toa Synthetic Co., Ltd. , "IXEPLAS-A2", "IXEPLAS-A3", "IXEPLAS-B1", etc., "DHT-4A", "DHT-4A-2", "DHT-4C", etc. manufactured by Kyowa Chemical Industry Co., Ltd. ..

The content of the ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth is based on 100 parts by mass of the curable composition in terms of solid content. It is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.02 parts by mass or more and 5 parts by mass or less, and further preferably 0.03 parts by mass or more and 3 parts by mass or less. When the content of the ion scavenger is within the above numerical range, a curable composition having excellent flexibility and resolution and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions can be obtained. be able to.

[(B) Photosensitive monomer]
(B) The photosensitive monomer is a monomer having an ethylenically unsaturated double bond. As the photosensitive monomer, for example, monofunctional (meth) acrylate and polyfunctional (meth) acrylate can be used. As the polyfunctional (meth) acrylate, bifunctional (meth) acrylate and trifunctional or higher functional (meth) acrylate can be used. In addition, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions. The photosensitive monomer may be used alone or in combination of two or more, but it is preferable to use two or more in combination.

Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and 2-hydroxy. Examples thereof include (meth) acrylates such as ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate and glycidyl methacrylate, and acryloyl morpholine.

Examples of the bifunctional (meth) acrylate include diols such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate. Diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol di. Diacrylate of diol obtained by adding at least one of ethylene oxide and propylene oxide to acrylate and neopentyl glycol, diacrylate of glycol such as caprolactone-modified neopentyl glycol diacrylate modified hydroxypivalate, and bisphenol A EO adduct. Examples thereof include diacrylate, bisphenol A PO adduct diacrylate, tricyclodecanedimethanol diacrylate, hydrogenated dicyclopentadienyl diacrylate, and diacrylate having a cyclic structure such as cyclohexyl diacrylate.

Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, and epichlorohydrin-modified trimethylolpropane triacrylate. , Pentaerythritol tetraacrylate, tetramethylolmethane tetraacrylate, ethylene oxide-modified phosphoric acid triacrylate, propylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, or sill thereof. Examples thereof include polyfunctional acrylates typified by sesquioxane-modified products, metaacrylate monomers corresponding thereto, and εcaprolactone-modified trimethyloloxyethyl isocyanurate.

The blending amount of the photosensitive monomer is preferably 30 parts by mass or more and 95 parts by mass or less, and more preferably 30 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the curable composition in terms of solid content. .. When the blending amount of the photosensitive monomer is within the above numerical range, a curable composition having excellent flexibility and resolution and excellent adhesion to copper after being left for a long period of time under high temperature and high humidity conditions can be obtained. be able to.

[(C) Photopolymerization Initiator]
The photopolymerization initiator is for reacting the (B) photosensitive monomer by exposure. Any known photopolymerization initiator can be used. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.

Specific examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis. -(2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide , Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, Bis- (2, Bisacylphosphine oxides such as 4,6-trimethylbenzoyl) -phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethyl Monoacylphosphine oxides such as benzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; phenyl ( 2,4,6-trimethylbenzoyl) ethyl phosphinate, 1-hydroxy-cyclohexylphenylketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1- On, 2-hydroxy-1-{4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1 -Hydroxyacetophenones such as phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; benzoin alkyl ethers; benzophenone , P-Methylbenzophenone, Michler's ketone, Methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone and other benzophenones; acetphenone, 2,2-dimethoxy-2-phenyl Acetphenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4- (4- (4-) Morphorinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone and other acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chloro Thioxanthones such as thioxanthone and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-aminoanthraquinone and the like. Anthraquinones; Ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p-dimethylbenzoic acid ethyl ester; 1,2 -Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] Oxim esters such as-, 1- (O-acetyloxime); bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) ) Phenyl) Titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyll-1-yl) ethyl) phenyl] Titanocenes such as titanium; phenyldisulfide 2-nitro Examples thereof include fluorene, butyloin, anisoine ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like.

Examples of commercially available α-aminoacetophenone-based photopolymerization initiators include Omnirad 907, 369, 369E, 379 manufactured by IGM Resins. Examples of commercially available acylphosphine oxide-based photopolymerization initiators include Omnirad TPO H and 819 manufactured by IGM Resins. Commercially available products of oxime ester-based photopolymerization initiators include Irgacure OXE01 and OXE02 manufactured by BASF Japan Ltd., N-1919 manufactured by ADEKA Corporation, ADEKA Arkuru's NCI-831, NCI-831E, and Changzhou Powerful Electronics New Materials Co., Ltd. TR-PBG-304 and the like can be mentioned.

In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-22007, JP-A-2006-160634, JP-A-2008-09470, JP-A-2008-50967, Examples thereof include carbazole oxime ester compounds described in JP-A-2009-040762 and JP-A-2011-80036.

The amount of the photopolymerization initiator to be blended is not particularly limited, but is preferably 0.2 parts by mass or more and 25 parts by mass or less, more preferably 0 parts by mass, based on 100 parts by mass of the curable composition in terms of solid content. It is 5 parts by mass or more and 20 parts by mass or less.

A photoinitiator or sensitizer may be used in combination with the above-mentioned (C) photopolymerization initiator. Examples of the photoinitiator aid or sensitizer include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds and the like. In particular, it is preferable to use thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone. By including the thioxanthone compound, the deep curability can be improved. Although these compounds may be used as a photopolymerization initiator, they are preferably used in combination with a photopolymerization initiator. In addition, one type of photoinitiator aid or sensitizer may be used alone, or two or more types may be used in combination.

[(D) Thermosetting component]
Any known thermosetting component (D) can be used. Since the curable composition contains a thermosetting component, the heat resistance of the cured film can be improved. Examples of the heat-curable component include amino resins such as melamine resin, benzoguanamine resin, melamine derivative, and benzoguanamine derivative, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimide, and carbodiimide resins. Known thermocuring components can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule. As the thermosetting component, one type may be used alone or two or more types may be used in combination.

The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4, or 5-membered cyclic (thio) ether groups in the molecule, and is, for example, a plurality of compounds in the molecule. Examples thereof include a compound having an epoxy group, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin.

Examples of such epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, and phenol novolac type epoxy resin. Examples thereof include cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, and triphenylmethane type epoxy resin.
Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate are added to the hydroxyl group of the epoxy acrylate resin. Epoxy urethane acrylate compounds obtained by reacting a half urethane compound may also be mentioned.

Examples of commercially available epoxy resins include jER 828, 806, 807, YX8000, YX8034, 834 manufactured by Mitsubishi Chemical Corporation, YD-128, YDF-170, ZX-1059 manufactured by Nittetsu Chemical & Materials Co., Ltd. Examples thereof include ST-3000, EPICLON 830, 835, 840, 850, N-730A, N-695 manufactured by DIC Corporation, and RE-306 manufactured by Nippon Kayaku Corporation.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, and 1,4-bis [(3-3-oxythenylmethoxy) methyl] ether. Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-3) Oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and polyfunctional oxetane such as their oligomers or copolymers, as well as oxetane alcohols and novolak resins. , Poly (p-hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, etherified products with a resin having a hydroxyl group such as silsesquioxane, and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate can also be mentioned.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin and the like. Further, using the same synthesis method, an episulfide resin or the like in which the oxygen atom of the epoxy group of the novolak type epoxy resin is replaced with a sulfur atom can also be used.

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycol uryl compounds and methylol urea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. Polyisocyanate compounds include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolyrene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; bicyclo Alicyclic polyisocyanates such as heptanthriisocyanate; and adducts, burettes, and isocyanurates of the isocyanate compounds mentioned above can be mentioned.

As the blocked isocyanate compound, an addition reaction product of the isocyanate compound and the isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the above-mentioned polyisocyanate compound and the like. Examples of the isocyanate blocking agent include a phenol-based blocking agent; a lactam-based blocking agent; an active methylene-based blocking agent; an alcohol-based blocking agent; an oxime-based blocking agent; a mercaptan-based blocking agent; an acid amide-based blocking agent; an imide-based blocking agent; Amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents and the like can be mentioned.

The amount of the thermosetting component (D) to be blended is not particularly limited, but is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 5 parts by mass, with respect to 100 parts by mass of the curable composition in terms of solid content. It is 25 parts by mass or less.

[(E) Colorant]
The curable composition of the present invention may contain (E) a colorant. The colorant is not particularly limited, and known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used, but it may reduce the environmental load and affect the human body. It is preferable that the colorant does not contain halogen from the viewpoint of less.

Examples of red colorants include monoazo, disazo, azolake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, quinacridone, etc. -Index (CI; The Society of Dyers and Colorists (issued by The Society of Dyersand Colorists)) numbered ones can be mentioned.

As a monoazo red colorant, Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114, 146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269 and the like can be mentioned. Examples of the disazo-based red colorant include Pigment Red 37, 38, 41 and the like. Further, as a monoazolake-based red colorant, Pigment Red 48: 1,48: 2,48: 3,48: 4,49: 1,49: 2,50: 1,52: 1,52: 2,53: Examples thereof include 1,53: 2,57: 1,58: 4,63: 1,63: 2,64: 1,68. Examples of the benzimidazolone-based red colorant include Pigment Red 171, 175, 176, 185, 208 and the like. Examples of the perylene-based red colorant include Solvent Red 135,179, Pigment Red 123,149,166,178,179,190,194,224 and the like. Examples of the diketopyrrolopyrrole-based red colorant include Pigment Red 254, 255, 264, 270, 272 and the like. Examples of the condensed azo red colorant include Pigment Red 220, 144, 166, 214, 220, 211, 242 and the like. Examples of the anthraquinone-based red colorant include Pigment Red 168, 177, 216 and Solvent Red 149, 150, 52, 207. Examples of the quinacridone-based red colorant include Pigment Red 122, 202, 206, 207, 209 and the like.

Examples of the blue colorant include phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds include compounds classified as Pigment. For example, Pigment Blue 15,15: 1,15: 2,15: 3,15: 4,15: 6,16,60. As the dye system, Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 and the like can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used.

Examples of the yellow colorant include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, etc. For example, the anthraquinone yellow colorant includes Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202 and the like can be mentioned. Examples of the isoindolinone-based yellow colorant include Pigment Yellow 110, 109, 139, 179, 185 and the like. Pigment Yellow as a condensed azo yellow colorant
93, 94, 95, 128, 155, 166, 180 and the like can be mentioned. Examples of the benzimidazolone-based yellow colorant include Pigment Yellow 120, 151, 154, 156, 175, 181 and the like. In addition, as a monoazo yellow colorant, Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62: 1,65,73,74,75,97,100, 104, 105, 111, 116, 167, 168, 169, 182, 183 and the like can be mentioned. Examples of the disazo-based yellow colorant include Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198 and the like. Can be mentioned.

In addition, colorants such as purple, orange, brown, black, and white may be added. Specifically, Pigment Black 1,6,7,8,9,10,11,12,13,18,20,25,26,28,29,30,31,32, Pigment Violet 19, 23,29 , 32, 36, 38, 42, Solvent Violet 13, 36, C.I. I. Pigment Orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73, PigmentBrown 23,25, Carbon Black, Examples include titanium oxide.

The amount of the colorant (E) to be blended is not particularly limited, but is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0, with respect to 100 parts by mass of the curable composition in terms of solid content. It is 0.05 parts by mass or more and 10 parts by mass or less, and more preferably 0.1 parts by mass or more and 5 parts by mass or less.

[Other additive ingredients]
If necessary, the curable composition of the present invention further includes an organic solvent, a photoinitiator, a cyanate compound, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion accelerator, a block copolymer, and a chain. Transfer agents, polymerization inhibitors, antioxidants, surface tension modifiers, rust preventives, fine powder silica, organic bentonite, thickeners such as montmorillonite, silicone-based, fluorine-based, polymer-based defoaming agents and / or Ingredients such as leveling agents, silane coupling agents such as imidazole, thiazole, and triazole, flame retardants such as phosphinates, phosphoric acid ester derivatives, and phosphorus compounds such as phosphazene compounds can be blended. As these, those known in the field of electronic materials can be used.

[Physical characteristics]
The curable composition of the present invention preferably has a viscosity suitable for the printing method to be used in consideration of workability, and more preferably has a viscosity suitable for inkjet printing. For example, the viscosity of the curable composition at 50 ° C. is preferably 50 mPa · s or less, more preferably 20 mPa · s or less. The viscosity of the curable composition shall be 50 ° C., 100 rpm, 30 seconds value according to 10 "Conical-Viscosity measurement method by flat plate type rotational viscometer" of JIS Z 8803: 2011, and 1 ° 34'x as a cone rotor. It can be measured using a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) using R24.

[Use]
The curable composition according to the present invention is useful for forming a pattern layer as a permanent coating of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and is particularly useful for forming a solder resist. Further, since the curable composition of the present invention can form a cured product having excellent film strength even with a thin film, a pattern on a printed wiring board, for example, a package substrate (printed wiring board used for a semiconductor package), which is required to be thinned. It can also be suitably used for forming a layer. Further, the cured product obtained from the curable composition of the present invention is excellent in flexibility and can be suitably used for a flexible printed wiring board.

Further, the curable composition according to the present invention can be used not only for forming a pattern layer of a cured film but also for an application not forming a pattern layer, for example, a molding application (sealing application).

[Cured product]
The cured product of the present invention is obtained by curing the above-mentioned curable composition of the present invention. In particular, the cured product of the present invention is preferably obtained by curing the above-mentioned curable composition of the present invention by inkjet printing using an inkjet printer. More specifically, the cured product of the present invention can be obtained by irradiating the curable composition immediately after printing with light and photo-curing it. Light 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, for example, by attaching a light source such as a high-pressure mercury lamp, a metal halide lamp, or an ultraviolet LED to the side surface of the print head, and scanning by moving the print head or the base material. In this case, printing and ultraviolet irradiation can be performed almost at the same time. The inkjet printer can be performed by appropriately adjusting conventionally known conditions, and either the piezo method or the thermal method can be used, but the piezo method is preferable. The cured product of the present invention can be suitably used for printed wiring boards, electrical and electronic parts, and the like. Since the cured product of the present invention has excellent flexibility, it can be particularly preferably used for a flexible printed wiring board.

[Printed wiring board]
The printed wiring board of the present invention comprises a cured product obtained by curing the curable composition of the present invention.

The base material includes a printed wiring board and a flexible printed wiring board whose circuit is formed of copper or the like in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, and glass cloth / paper epoxy. , Synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc. are used for high-frequency circuit copper-clad laminates, etc., and all grades (FR-4, etc.) of copper-clad laminates are used. Examples thereof include a plate, a metal substrate, a polyimide film, a polyethylene terephthalate film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and Comparative Examples. In the following, "part" and "%" are all based on mass unless otherwise specified.

[Examples 1 to 6, Comparative Examples 1 and 2]
<Preparation of curable composition>
Using a conical bead mill K-8 (manufactured by Buhra) for a solution prepared by adding 4 parts by mass of 1,9-nonanediol diacrylate to 1 part by mass of the ion scavenger shown in Table 1, zirconia beads (beads). The bead mill dispersion was performed for 2 hours under the conditions of a particle size of 0.65 mm), a rotation speed of 1000 rpm, a discharge rate of 20%, and a filling rate of 88% to obtain a slurry in which an ion scavenger was dispersed (IXEPLAS-A1: D _50). = 0.46 μm, DHT-4A: D ₅₀ = 0.34 μm, KE-S S50: D ₅₀ = 0.48 μm, dynamic light scattering particle size distribution measuring device Nanotrac Wave II UT151 (manufactured by Microtrack Bell) Measured). Then, using the prepared slurry, each component was blended at the ratio shown in Table 1 (solid content mass, unit: parts by mass), stirred with a dissolver, and dispersed again using a bead mill for 2 hours. A curable composition was obtained.

<Viscosity measurement of curable composition>
The viscosities of the curable compositions of Examples 1 to 6 and Comparative Examples 1 and 2 are 50 ° C., 100 rpm, and 30 seconds according to 10 "Conical-Viscosity measurement method using a flat plate type rotational viscometer" of JIS Z 8803: 2011. The value was measured using a cone plate type viscometer (TVE-33H, manufactured by Toki Sangyo Co., Ltd.) using 1 ° 34'x R24 as the cone rotor. As a result, the curable compositions of Examples 1 to 6 and Comparative Examples 1 and 2 all had a viscosity of 50 mPas · s or less, and were suitable for inkjet use.

<Forming process of cured coating film for MIT test>
Prepare a flexible printed wiring board (base material thickness 25 μm, L / S = 200/200 μm, polyimide film, manufactured by Ube Industries, Ltd., Upirex) in which a circuit is formed with a copper thickness of 18 μm, and use MEC CB-801Y. Then, the pretreatment was performed by spraying a spray at 25 ° C. for 120 seconds so that the etching amount was 1 μm. Then, the curable compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were applied to the pretreated flexible printed wiring substrate with CP56151 (manufactured by Microcraft) and the array was KM1024iSHE (manufactured by Microcraft). Inkjet printing was performed using a droplet amount of 6 pL, a number of nozzles of 2 × 1024, and a head temperature of 50 ° C.) so that a solid portion could be formed. Subsequently, the coated flexible printed wiring board was temporarily cured under the condition of ^{300 mJ / cm 2} using an LED (SGHUV-UN-L042-B, manufactured by Microcraft Co., Ltd., wavelength 365 nm) as a light source. Subsequently, it was heated at 150 ° C. for 60 minutes in a hot air circulation type drying oven (manufactured by Yamato Scientific Co., Ltd., DF610) to form a cured coating film having a thickness of 20 μm.

A MIT test (R = 0.38 mm) was carried out on the obtained solid coating film using a MIT folding fatigue tester D type (manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS P8115. , Flexibility was evaluated. With a load (0.5 kgf) applied, the test piece was vertically attached to the clamp, bent at a bending angle of 135 degrees and a speed of 175 cpm, and the number of reciprocating bends (times) until breaking was measured. .. The evaluation criteria are as follows. The obtained evaluation results are shown in Table 1.
(Evaluation criteria for flexibility)
⊚: MIT resistance was 150 times or more.
◯: MIT resistance was 100 times or more and 149 times or less.
Δ: MIT resistance was 50 times or more and 99 times or less.
X: MIT resistance was 49 times or less.

<Forming process of cured coating film for adhesion / resolution test>
Prepare a copper-clad polyimide base material (base material thickness: 25 μm, manufactured by Nittetsu Chemical & Materials Co., Ltd., imide name Espanex) with a copper thickness of 12 μm and no circuit formed, and use MEC CB-801Y. Pretreatment was performed by spraying a spray at 25 ° C. for 120 seconds so that the etching amount was 1 μm. After that, the curable compositions of Examples 1 to 6 and Comparative Examples 1 and 2 were added to the solid portion of the pretreated flexible printed wiring substrate so that L / S = 100/100 μm and 130/130 μm. Inkjet printing was performed using CP56151 (manufactured by Microcraft) and an array of KM1024iSHE (manufactured by Microcraft, coating droplet amount 6 pL, number of nozzles 2 × 1024, head temperature 50 ° C.). Subsequently, the coated flexible printed wiring board was temporarily cured under the condition of ^{300 mJ / cm 2} using an LED (SGHUV-UN-L042-B, manufactured by Microcraft Co., Ltd., wavelength 365 nm) as a light source. Subsequently, it was heated at 150 ° C. for 60 minutes in a hot air circulation type drying oven (manufactured by Yamato Scientific Co., Ltd., DF610) to form a cured coating film having a thickness of 20 μm.
The formed line pattern was observed and the resolution was evaluated. The evaluation criteria are as follows. The obtained evaluation results are shown in Table 1.
(Evaluation criteria for resolution)
⊚: A line of L / S = 100/100 μm could be drawn.
〇: A line of L / S = 130/130 μm could be drawn.
X: A line of L / S = 130/130 μm could not be drawn.

Next, the obtained solid cured coating film was exposed to the obtained cured coating film at a temperature of 85 ° C. and a humidity of 85% for 500 hours, left at room temperature for 24 hours, and then cross-cut using each of the prepared wiring boards. A tape peel test was conducted. The 100 squares formed were peeled off with cellophane tape (adhesion strength of 10 ± 1N per 25 mm width), and the number of remaining squares was counted. The evaluation criteria are as follows. The obtained evaluation results are shown in Table 1.
(Evaluation criteria for adhesion)
⊚: The number of remaining squares was 100/100.
〇: The number of remaining cells was 90/100 or more and 99/100 or less.
X: The number of remaining cells was 89/100 or less.

The abbreviations in Table 1 are as follows.
-IXEPLAS-A1: Zr-Mg-Al system (manufactured by Toagosei Co., Ltd.)
-DHT-4A: Mg _4.3 Al ₂ (OH) _12.6 CO ₃ · nH ₂ O (n indicates the number of hydration and is 0 or a positive number) (manufactured by Kyowa Chemical Industry Co., Ltd.)
・ IBXA: Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ 4HBA: 4-Hydroxybutyl acrylate (manufactured by Nihon Kasei Co., Ltd.)
-A-TMPT: Trimethylolpropane triacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
・ 1,9-NDA: 1,9-nonanediol diacrylate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-DPGDA: Dipropylene glycol diacrylate (manufactured by Toyo Chemicals Co., Ltd.)
Omnirad 379: 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (manufactured by IGM Resins)
BI7982: Trifunctional Block Isocyanate (manufactured by Baxenden chemicals Limited)
-KE-S S50: Silica fine particles (manufactured by Nippon Shokubai Co., Ltd.)
-BYK-315N: Silicone-based surface conditioner (manufactured by Big Chemie Japan)
・ Pigment Blue15: 3: Phthalocyanine-based blue pigment ・ Pigment Yellow147: Anthraquinone-based yellow pigment

As is clear from Table 1, the curable composition of the examples of the present application was able to obtain a cured coating film having excellent flexibility and resolution and excellent adhesion to copper. In particular, such a curable composition was suitable for inkjet printing.

Claims (8)

1. (A) An ion scavenger containing at least one component selected from the group consisting of zirconium, aluminum, zinc, magnesium, calcium, antimony and bismuth.
   (B) Photosensitive monomer and
   (C) Photopolymerization initiator and
   A curable composition comprising.
2. (D) The curable composition according to claim 1, further containing a thermosetting component and containing a blocked isocyanate as a thermosetting component.
3. The curable composition according to claim 1 or 2, wherein the content of the ion scavenger is 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the curable composition.
4. The curable composition according to any one of claims 1 to 3, wherein the photosensitive monomer contains a monofunctional (meth) acrylate and a polyfunctional (meth) acrylate.
5. The curable composition according to any one of claims 1 to 4, wherein the viscosity at 50 ° C. is 50 mPa · s or less.
6. The curable composition according to any one of claims 1 to 5, which is used for inkjet printing.
7. A cured product, which is obtained by curing the curable composition according to any one of claims 1 to 6.
8. A printed wiring board comprising the cured product according to claim 7.