JPWO2019044803A1 - Epoxy resin modifier - Google Patents

Abstract

An object of the present invention is to provide a composition capable of achieving both heat resistance and low elastic modulus and capable of producing a cured product having excellent copper foil adhesion. The present invention is an active energy ray-curable composition containing an acid group-containing epoxy (meth)acrylate resin, an epoxy curing agent and a modifying resin, wherein the modifying resin is selected from the group consisting of a hydroxyl group and a carboxy group. It has at least one specific functional group, the modified resin has a glass transition temperature of −100° C. or higher and 50° C. or lower, and the modified resin has a number average molecular weight of 600 or higher and 50,000 or lower. The active energy ray-curable composition is used.

Description

  The present invention relates to an active energy ray-curable resin composition containing an epoxy resin modifier as a modifying resin, a solder resist, and a dry film and a printed wiring board obtained by using the same.

  Photocurable resin compositions are widely used as solder resists for printed wiring boards, and many required properties such as high heat resistance in cured products, excellent copper foil adhesion, and excellent dielectric properties There is. In particular, heat resistance, low elastic modulus, and copper foil adhesion become important characteristics due to miniaturization of wiring due to higher density and narrower pitch as electronic equipment becomes smaller, lighter, and more sophisticated.

  As an attempt to improve the properties of a cured product, an attempt has been made to add an elastomer to the photocurable resin composition (see Patent Document 1).

JP 2002-162738 A

  However, according to the studies by the present inventors, in a cured product formed from a conventional photocurable resin composition, although a low elastic modulus can be achieved by using a resin having a flexible skeleton, heat resistance Since (Tg) is lowered, insulation reliability is deteriorated, and it cannot be said that the copper foil adhesion is sufficient.

  An object of the present invention is to provide a composition capable of achieving both heat resistance and a low elastic modulus, and capable of producing a cured product having excellent copper foil adhesion.

  The present invention is an active energy ray-curable composition containing an acid group-containing epoxy (meth)acrylate resin, an epoxy curing agent and a modifying resin, wherein the modifying resin is selected from the group consisting of a hydroxyl group and a carboxy group. It has at least one kind, the glass transition temperature of the modified resin is −100° C. or higher and 50° C. or lower, and the number average molecular weight of the modified resin is 600 or higher and 50,000 or lower. And an active energy ray-curable composition.

  According to the active energy ray-curable resin composition of the present invention, it is possible to produce a cured product that has both heat resistance and a low elastic modulus, and that has excellent copper foil adhesion.

  The active energy ray-curable resin composition of the present invention contains an acid group-containing epoxy (meth)acrylate resin (A), an epoxy curing agent (B) and a modified resin (C). The active energy ray-curable resin composition may contain a polymerizable compound (D), a photopolymerization initiator (E), a photosensitizer (F), and may further contain a solvent (G). Good.

  In the present specification, an active energy ray means an ionizing radiation such as an ultraviolet ray; an electron beam; an α ray, a β ray, a γ ray. When the active energy rays are ultraviolet rays, the active energy ray-curable resin composition of the present invention preferably contains a photopolymerization initiator (E) and may further contain a photosensitizer (F). On the other hand, when the active energy ray is an electron beam or ionizing radiation, the active energy ray-curable resin composition of the present invention does not need to include the photopolymerization initiator (E) and the photosensitizer (F). ..

  The acid group-containing epoxy (meth)acrylate resin (A) is an epoxy (meth)acrylate resin having an acid group (preferably a carboxy group), and an epoxy resin having two or more epoxy groups in one molecule (hereinafter, A resin (A1) having a structure in which (meth)acrylic acid is added to the epoxy group of "a specific epoxy resin", and one or more divalent organic acids are further added; or The resin (A2) in which an acid-reactive (meth)acrylate compound such as glycidyl (meth)acrylate is further added to a part of the carboxy group of the resin (A1) is preferable.

As the specific epoxy resin, one kind or two or more kinds can be used, and bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol Novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol cocondensed novolac type epoxy resin, naphthol-cresol cocondensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol Examples thereof include aralkyl type epoxy resin and dicyclopentadiene-phenol addition reaction type epoxy resin.
Among them, from the viewpoint of heat resistance, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol cocondensed novolac type epoxy resin, naphthol-cresol cocontracted novolac type epoxy resin A novolac type epoxy resin such as a resin is preferable.
The total content of the novolac type epoxy resin and the cresol novolac type epoxy resin contained in the specific epoxy resin is preferably 90% by mass or more, more preferably 95% by mass or more in 100% by mass of the specific epoxy resin, The upper limit is 100% by mass.

  Examples of the organic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid. Examples thereof include anhydrides of dicarboxylic acids such as acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. As the dicarboxylic acid anhydride, from the viewpoint of heat resistance, anhydrous dicarboxylic acid having a cyclic structure such as fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. The thing is preferable.

  Examples of the acid-reactive (meth)acrylate compound include compounds having a glycidyl group such as glycidyl (meth)acrylate and a (meth)acryloyl group.

  The acid value of the acid group-containing epoxy (meth)acrylate resin (A) is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, More preferably, it is 90 mgKOH/g or less.

The weight average molecular weight of the acid group-containing epoxy (meth)acrylate resin (A) is preferably 3,000 or more, more preferably 5,000 or more, preferably 12,000 or less, more preferably 10,000 or less. Is. The molecular weight dispersity of the acid group-containing epoxy (meth)acrylate resin (A) is preferably 1.5 or more and 4 or less.
In the present specification, the weight average molecular weight means a value measured by gel permeation chromatography.

  The content of the acid group-containing epoxy (meth)acrylate resin (A) in the active energy ray-curable resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 18% by mass. It is above, preferably 90 mass% or less, more preferably 85 mass% or less, and further preferably 80 mass% or less.

  The epoxy curing agent (B) has a functional group (preferably an epoxy group) capable of reacting with an acid group (preferably a carboxy group) contained in the acid group-containing epoxy (meth)acrylate resin (A). Preferably. As the epoxy curing agent, one kind or two or more kinds can be used, and for example, the epoxy resins exemplified as the specific epoxy resin can be used. Among them, from the viewpoint of heat resistance, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol cocondensed novolac type epoxy resin, naphthol-cresol cocontracted novolac type epoxy resin A novolac type epoxy resin such as a resin is preferable, and one having a softening point of 50° C. or higher and 120° C. or lower is preferable.

  The epoxy group equivalent of the epoxy curing agent (B) is preferably 5 or more, more preferably 30 or more, still more preferably 50 or more, preferably 500 or less, more preferably 400 or less, still more preferably 300 or less. ..

  The content of the epoxy curing agent (B) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 100 parts by mass of the acid group-containing epoxy (meth)acrylate resin (A). The amount is 25 parts by mass or more, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and further preferably 50 parts by mass or less.

A curing accelerator (B1) may be used in combination with the epoxy curing agent (B). As the curing accelerator (B1), one kind or two or more kinds can be used, and examples thereof include phosphorus compounds such as triphenylphosphine; dicyanamide; benzyldimethylamine, 4-(dimethylamino)-N,N-. Amine compounds such as dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine; imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4- Cyclic amine compounds such as methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; adipic acid dihydrazide, sebacic acid Examples thereof include hydrazine compounds such as dihydrazide; organic acid metal salts; Lewis acids; amine complex salts.
The content of the curing accelerator (B1) is preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the epoxy curing agent (B).

The modified resin (C) has at least one specific functional group selected from the group consisting of a hydroxyl group and a carboxy group. The functional group value of the specific functional group contained in the modified resin (C) is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, further preferably 18 mgKOH/g or more, and preferably 200 mgKOH/g. Or less, more preferably 150 mgKOH/g or less, still more preferably 120 mgKOH/g or less.
The functional group value represents a hydroxyl value when the specific functional group is only a hydroxyl group, and represents an acid value when the specific functional group is only a carboxy group. When the specific functional group contains both a hydroxyl group and a carboxy group, it represents the total of the hydroxyl value and the acid value.

  The number of specific functional groups contained in the modified resin (C) is preferably 2 or more per molecule, preferably 6 or less, more preferably 4 or less, and further preferably 3 or less. , Particularly preferably two.

  The modified resin (C) is preferably at least one selected from the group consisting of polyester resins and polyurethane resins, and more preferably polyester resins.

  As said polyester resin, 1 type(s) or 2 or more types can be used, for example, polyester resin obtained by reacting a polyol and polycarboxylic acid; Polyester resin obtained by ring-opening polymerization reaction of a cyclic ester compound. A polyester resin or the like obtained by copolymerizing these;

As the polyol used for producing the polyester resin, one kind or two or more kinds can be used, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol. , An aliphatic polyol such as 1,3-butanediol; a polyol having an alicyclic structure such as cyclohexanedimethanol; a polyol having an aromatic structure such as bisphenol A and bisphenol F; and an alkylene oxide having a polyol having the aromatic structure. Examples include modified polyols.
Among them, a polyol having the alicyclic structure, a polyol having the aromatic structure and a polyol obtained by alkylene oxide modification of the polyol having the aromatic structure are preferable, and a polyol obtained by modifying the polyol having the aromatic structure with alkylene oxide is more preferable. preferable.

  The molecular weight of the polyol is preferably 50 or more, preferably 1,500 or less, more preferably 1,000 or less, still more preferably 700 or less.

  Examples of the alkylene oxide used for modifying the polyol having an aromatic structure include alkylene oxides having 2 to 4 carbon atoms (preferably 2 to 3 carbon atoms) such as ethylene oxide and propylene oxide. The number of moles of the alkylene oxide added is preferably 2 mol or more, more preferably 4 mol or more, preferably 20 mol or less, more preferably 16 mol or less with respect to 1 mol of the polyol having an aromatic structure. is there.

As said polycarboxylic acid, 1 type(s) or 2 or more types can be used, for example, aliphatic polycarboxylic acid, such as succinic acid, adipic acid, sebacic acid, and dodecane dicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, Aromatic polycarboxylic acids such as naphthalenedicarboxylic acid; anhydrides or esterified products thereof.
Above all, it is preferable to contain an aliphatic polycarboxylic acid. The content of the aliphatic polycarboxylic acid is preferably 5 mol% or more, more preferably 10 mol% or more, and preferably 100 mol% or less in the total of the polycarboxylic acids.
It is also a preferred embodiment that the polycarboxylic acid contains an aliphatic polycarboxylic acid and an aromatic polycarboxylic acid. The content ratio of the aromatic polycarboxylic acid and the aliphatic polycarboxylic acid is preferably 1/99 or more, more preferably 30/70 or more, still more preferably 50/50 or more, and preferably 99 on a molar basis. /1 or less, more preferably 90/10 or less, and further preferably 85/15 or less.

  The content ratio (polyol/polycarboxylic acid) of the polyol and the polycarboxylic acid used in the production of the polyester resin is preferably 20/80 or more, more preferably 30/70 or more, still more preferably 40 on a mass basis. /60 or more, preferably 99/1 or less, more preferably 90/10 or less, and further preferably 85/15 or less.

  As the cyclic ester compound, one kind or two or more kinds can be used, and for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, ε-methylcaprolactone, ε-ethylcaprolactone, ε. Examples include -propylcaprolactone, 3-pentene-4-olide, 12-dodecanolide and γ-dodecanolactone.

  The content of oxyalkylene units having 4 or more carbon atoms contained in the polyester resin is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less. Is.

  The polyester resin can be produced, for example, by reacting the polyol with the polycarboxylic acid. The reaction temperature is preferably 190°C or higher, more preferably 200°C or higher, preferably 250°C or lower, more preferably 240°C or lower. The reaction time is preferably 1 hour or more and 100 hours or less.

A catalyst may coexist during the reaction. As said catalyst, 1 type(s) or 2 or more types can be used, for example, titanium type catalysts, such as tetraisopropyl titanate and tetrabutyl titanate; tin type catalysts, such as dibutyltin oxide; organic sulfones, such as p-toluenesulfonic acid. Examples thereof include acid catalysts.
The amount of the catalyst is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and preferably 0.01 parts by mass, with respect to 100 parts by mass in total of the polyol and the polycarboxylic acid. Hereafter, it is more preferably 0.005 parts by mass or less.

  The polyurethane resin is a reaction product of a polyol and a polyisocyanate, and has a hydroxy group at the terminal.

  Examples of the polyol used for producing the polyurethane resin include polyether polyol, polyester polyol, and polycarbonate polyol.

  Examples of the polyether polyol include those obtained by subjecting one or more compounds having two or more active hydrogen atoms as an initiator to addition polymerization (ring opening polymerization) of an alkylene oxide.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4- Linear diols such as butanediol and 1,6-hexanediol; branched chain diols such as neopentyl glycol; triols such as glycerin, trimethylolethane, trimethylolpropane and pyrogallol; polyols such as sorbitol, sucrose and aconit sugar Tricarboxylic acids such as aconitic acid, trimellitic acid and hemimellitic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propanetri Thiol etc. are mentioned.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like.

  As the polyether polyol, polyoxytetramethylene glycol obtained by addition-polymerizing (ring-opening polymerization) tetrahydrofuran with the initiator is preferable.

  Examples of the polyester polyols include polyester polyols obtained by esterifying a low molecular weight polyol (for example, a polyol having a molecular weight of 50 or more and 300 or less) and a polycarboxylic acid; a ring-opening polymerization of a cyclic ester compound such as ε-caprolactone. Polyester polyols obtained by reaction; copolymerized polyester polyols thereof and the like can be mentioned.

  As the low molecular weight polyol, a polyol having a molecular weight of about 50 or more and about 300 or less can be used. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol. , 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol and other aliphatic polyols having 2 to 6 carbon atoms; 1,4-cyclohexanediol, cyclohexane Examples thereof include alicyclic structure-containing polyols such as dimethanol; bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; Examples thereof include anhydrides or ester-forming derivatives of group polycarboxylic acids and aromatic polycarboxylic acids.

  Examples of the polycarbonate polyol include a reaction product of a carbonic acid ester and a polyol; a reaction product of phosgene and bisphenol A and the like.

  Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.

  Examples of the polyol capable of reacting with the carbonate ester include polyols exemplified as the low molecular weight polyols; high-molecular weight polyols such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.) and polyester polyols (polyhexamethylene adipate, etc.) The average molecular weight is 500 or more and 5,000 or less).

  The number average molecular weight of the polyol used for producing the polyurethane resin is preferably 500 or more, more preferably 700 or more, preferably 3,000 or less, more preferably 2,000 or less.

  As said polyisocyanate, 1 type(s) or 2 or more types can be used, for example, 4,4'- diphenylmethane diisocyanate, 2,4'- diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, triene diisocyanate. Aromatic polyisocyanates such as naphthalene diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; cyclohexane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate Examples thereof include alicyclic structure-containing polyisocyanate.

  The equivalent ratio [isocyanate group/hydroxyl group] of the hydroxyl group of the polyol used in the production of the urethane resin and the isocyanate group of the polyisocyanate is preferably 0.1 or more, more preferably 0.2 or more on a molar basis. Yes, preferably 0.9 or less, more preferably 0.7 or less.

  The polyurethane resin can be produced by reacting the polyol and the polyisocyanate used for producing the polyurethane resin. When the terminal of the obtained polyurethane resin is an isocyanate group, a chain extender having a hydroxy group may be further reacted.

  As the chain extender having a hydroxy group, one kind or two or more kinds can be used, and for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol. , 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, sorbitol and other glycol compounds; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy Examples thereof include phenol compounds such as diphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; water and the like.

  The glass transition temperature of the modified resin (C) is −100° C. or higher, preferably −80° C. or higher, more preferably −70° C. or higher, 50° C. or lower, preferably 40° C. or lower, more preferably It is preferably 30° C. or lower.

The number average molecular weight of the modified resin (C) is 500 or more, preferably 1,000 or more, more preferably 1,500 or more, 50,000 or less, preferably 30,000 or less, It is preferably 20,000 or less, more preferably 15,000 or less.
The number average molecular weight of the modified resin (C) can be calculated based on the functional group value.

  The modified resin (C) (epoxy resin modifier) is at least one resin selected from the group consisting of polyester resins and polyurethane resins, and is at least one selected from the group consisting of hydroxyl groups and carboxy groups. It preferably has a specific functional group, a glass transition temperature of −100° C. or higher and 50° C. or lower, and a number average molecular weight of 600 or higher and 50,000 or lower.

  The modified resin (C) of the present invention has the above-mentioned constitution, and is composed of only the soft segment and does not contain the hard segment (a component capable of aggregating to form the hard segment domain). The modified resin (C) of the present invention is capable of adjusting its affinity with an epoxy resin while maintaining its own chemical and mechanical properties. In the active energy ray-curable resin composition, Since it can be uniformly dispersed, it is considered that it is possible to provide both a heat resistance and a low elastic modulus, and to provide a cured product having excellent copper foil adhesion.

  The content of the modified resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass with respect to 100 parts by mass of the acid group-containing epoxy (meth)acrylate resin. The amount is at least 20 parts by mass, preferably at most 20 parts by mass, more preferably at most 15 parts by mass, still more preferably at most 12 parts by mass.

  The polymerizable compound (D) is a compound having a group (preferably a polymerizable double bond) that can be polymerized by an active radical, and is preferably a compound having a (meth)acryloyl group.

  As the polymerizable compound (D), a monofunctional compound such as phenoxy (meth)acrylate; 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Triethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, bis((meth)acryloyloxyethyl)ether of bisphenol A and 3-methylpentanediol di(meth)acrylate, methoxytetraethylene glycol di(meth) ) Bifunctional compounds such as acrylate and polyethylene glycol di(meth)acrylate and their ethylene oxide modified products, propylene oxide modified products and caprolactone modified products; trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris( Trifunctional compounds such as 2-(meth)acryloyloxyethyl) isocyanurate and ethylene oxide modified products, propylene oxide modified products and caprolactone modified products thereof; tetrafunctional compounds such as pentaerythritol tetra(meth)acrylate and ethylene oxide modified products thereof. , Propylene oxide modified products and caprolactone modified products; compounds having pentafunctionality such as dipentaerythritol penta(meth)acrylate and ethylene oxide modified products, propylene oxide modified products and caprolactone modified products thereof; dipentaerythritol hexa(meth)acrylate, etc. Hexafunctional compounds and their ethylene oxide modified products, propylene oxide modified products and caprolactone modified products; tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca Hexafunctional or higher-functional compounds such as (meth)acrylate, and ethylene oxide-modified products, propylene oxide-modified products and caprolactone-modified products thereof can be mentioned.

  The number average molecular weight of the polymerizable compound (D) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

  When the polymerizable compound (D) is contained, the content thereof is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the acid group-containing epoxy (meth)acrylate resin. It is more preferably 3 parts by mass or more, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 7 parts by mass or less.

As said photoinitiator (E), 1 type(s) or 2 or more types can be used, for example, diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo {2-. Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4- (2-Hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-butanone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(4-hydroxyethoxy)-phenyl]-2 -Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1 Acetophenone compounds such as -one; benzoin, benzoin methyl ether, benzoin isopropyl ether and other benzoin compounds; 2,4,6-trimethylbenzoindiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc. Acyl phosphine oxide compound; benzyl (dibenzoyl), methylphenylglyoxy ester, oxyphenylacetic acid 2-(2-hydroxyethoxy)ethyl ester, oxyphenylacetic acid 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester, etc. A benzyl compound of benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenylsulfide, acrylated benzophenone, 3,3′, Benzophenone compounds such as 4,4′-tetra(t-butylperoxycarbonyl)benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone and 4-methylbenzophenone; 2-isopropylthioxanthone, Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone Compounds: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2- Aminoalkylphenone compounds such as (dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Michler-ketone, 4,4′-diethylamino Aminobenzophenone compounds such as benzophenone; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl) )-9H-carbazol-3-yl]-, 1-(O-acetyloxime) and other oxime ester compounds; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone , Camphorquinone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, and the like.
When the photopolymerization initiator (E) is used, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, based on 100 parts by mass of the acid group-containing epoxy (meth)acrylate resin. The amount is preferably 5 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.

As the photosensitizer (F), one kind or two or more kinds can be used, and examples thereof include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, and the like. Examples thereof include sulfur diethyl compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfonate.
When the photosensitizer (F) is used, its content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 100 parts by mass of the photopolymerization initiator (E). It is 5 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 12 parts by mass or less.

  As said solvent (G), 1 type(s) or 2 or more types can be used, for example, ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons. , Petroleum-based solvents and the like. Specifically, for example, ketone solvents such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, tetramethylbenzene and Solvesso 150; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol. , Glycol ether solvents such as propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; dipropylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (carbitol acetate), diethylene glycol monobutyl ether acetate and other glycol ether acetate solvents; ethyl acetate, butyl acetate and other ester solvents; ethanol, propanol, ethylene glycol, propylene glycol and other alcohols Solvents; aliphatic hydrocarbon solvents such as octane and decane; petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

  The content of the solvent (G) in the active energy ray-curable resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and preferably 80% by mass. % Or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

  The active energy ray-curable resin composition may further contain a colorant. As the colorant, one kind or two or more kinds can be used, and any of a pigment, a dye and a natural pigment may be used. As the hue of the colorant, any colorant classified by color index into red, orange, yellow, green, blue, purple, black and the like can be used.

  The active energy ray-curable resin composition may include a filler. As said filler, 1 type(s) or 2 or more types can be used, For example, an organic filler; Inorganic fillers, such as barium sulfate, spherical silica, and talc, are mentioned.

  The active energy ray-curable resin composition may further contain other additives such as a thermal polymerization inhibitor and a thickener.

The active energy ray-curable resin composition can be used as the solder resist of the present invention.
A dry film formed from the solder resist of the present invention is also included in the technical scope of the present invention. The dry film can be produced, for example, by applying the solder resist on a substrate and removing the solvent (G) contained as necessary by drying or the like to form a resin layer. A blade coater, a lip coater, a comma coater, a film coater, or the like can be used for the coating. The drying temperature is preferably 60° C. or higher and 100° C. or lower.

  The thickness of the dry film is preferably 1 μm or more, more preferably 5 μm or more, preferably 200 μm or less, more preferably 100 μm or less.

  A printed wiring board having a cured product of a resin layer formed from the active energy ray-curable resin composition as an insulating resin layer is also included in the technical scope of the present invention. The printed wiring board can be produced, for example, by forming a resin layer of the active energy ray-curable resin composition on a base material and curing the resin layer. The curing is preferably performed by heat curing, and the curing temperature is preferably 140°C or higher and 180°C or lower.

  When the resin insulating layer is formed by a dry coating film obtained by applying and drying a photosensitive curable resin layer or a curable resin composition, the curable resin layer or the dry coating film formed on the base material (substrate) may be used. The film is exposed by a contact type (or non-contact type) through a photomask on which a pattern is formed, selectively by active energy rays or directly by a laser direct exposure machine. In the curable resin layer and the dried coating film, the exposed portion (the portion irradiated with the active energy ray) is cured. The drying temperature is preferably, for example, 60° C. or higher and 120° C. or lower.

  As an exposure machine used for active energy ray irradiation, a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser based on CAD data from a computer), an exposure device equipped with a metal halide lamp, and a (super) high pressure mercury lamp It is possible to use an installed exposure machine, an exposure machine equipped with an LED, and an exposure apparatus equipped with a mercury short arc lamp.

As the active energy ray, it is preferable to use light having a maximum wavelength in the range of 350 to 410 nm. By setting the maximum wavelength within this range, radicals can be efficiently generated from the photopolymerization initiator. The amount of exposure varies depending on the film thickness and the like, but can be generally in the range of 5 to 500 mJ/cm ² , and preferably 10 to 300 mJ/cm ² .

  As the direct drawing device, for example, those manufactured by Nippon Orbotech Co., Ltd., Pentax Co., Ltd., Oak Co., Ltd., Dainippon Screen Co., Ltd., or the like can be used, and the maximum energy wavelength is 350 to 410 nm. Any device may be used as long as it is a device for irradiating.

  Then, by exposing the curable resin layer or the dried coating film in this manner to cure the exposed portion (the portion irradiated with the active energy rays), the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0. By developing with a 3 to 3 wt% sodium carbonate aqueous solution), a pattern is formed on the curable resin layer or the dried coating film.

  At this time, the developing method may be a dipping method, a shower method, a spray method, a brush method, or the like. As the developing solution, an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines or the like can be used.

Furthermore, by heating the curable resin layer to a temperature of 140° C. or higher and 200° C. and thermally curing it, the carboxy group of the acid group-containing epoxy (meth)acrylate resin (A) and the epoxy curing agent (B) are separated. By reacting, a resin insulating layer (pattern) having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and insulation reliability can be formed.

  The total film thickness of the resin insulating layer in the printed wiring board of the present invention is preferably 100 μm or less, more preferably 5 to 50 μm.

  As the base material, in addition to a printed wiring board or a flexible printed wiring board on which a circuit is formed in advance, paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/non-woven cloth-epoxy resin , Glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluororesin/polyethylene/polyphenylene ether, polyphenylene oxide/cyanate ester, etc. A polyimide film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, or the like can be used.

  The resin insulating layer included in the printed wiring board of the present invention is suitable as a permanent coating, and particularly suitable as a solder resist.

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Synthesis Example 1] Synthesis of Polyester Resin A 772.3 parts by mass of bisphenol A type glycol ether (manufactured by DIC Corporation, "HYPROX (registered trademark) MDB-561") and adipic acid (hereinafter " 146.2 parts by mass were charged, and temperature rising and stirring were started.
Then, after raising the internal temperature to 230° C., 0.10 parts by mass of tetraisopropyl titanate (hereinafter referred to as “TiPT”) was charged as a catalyst and reacted at 230° C. for 24 hours to synthesize a polyester resin.
The hydroxyl value of the obtained polyester resin was 37.4 mgKOH/g (hereinafter abbreviated as a unit), the number average molecular weight was 3,000, and the glass transition temperature was -27°C.

[Synthesis Example 2] Synthesis of Polyester Resin B In a reaction apparatus, 779.1 parts by mass of bisphenol A type glycol ether ("HYPROX (registered trademark) MDB-561" manufactured by DIC Corporation) and isophthalic acid (hereinafter referred to as " 132.9 parts by mass of "iPA") and 40.4 parts by mass of sebacic acid (hereinafter referred to as "SebA") were charged, and heating and stirring were started.
Next, after raising the internal temperature to 230° C., 0.10 parts by mass of TiPT was charged and reacted at 230° C. for 24 hours to synthesize a polyester resin.
The obtained polyester resin had a hydroxyl value of 36.9, a number average molecular weight of 3,040, and a glass transition temperature of -14°C.

[Synthesis Example 3] Synthesis of Polyester Resin C 596.8 parts by mass of bisphenol A type glycol ether (manufactured by DIC Corporation, "HYPROX (registered trademark) MDB-561") and 257.4 parts of SebA were placed in a reactor. Mass parts were charged, and heating and stirring were started.
Next, after raising the internal temperature to 230° C., 0.10 parts by mass of TiPT was charged and reacted at 230° C. for 24 hours to synthesize a polyester resin.
The obtained polyester resin had an acid value of 36.6, a number average molecular weight of 3,070 and a glass transition temperature of -33°C.

[Synthesis Example 4] Synthesis of polyester resin D 430.9 parts by mass of 3-methyl-1,5-pentanediol and 629.4 parts by mass of SebA were charged into a reactor, and heating and stirring were started.
Then, after raising the internal temperature to 230° C., 0.03 parts by mass of TiPT was charged and a condensation reaction was carried out at 230° C. for 24 hours to synthesize a polyester resin.
The hydroxyl value of the obtained polyester resin was 24.6, the number average molecular weight was 4,560, and the glass transition temperature was -63°C.

[Synthesis Example 5] Synthesis of Urethane Resin A 1000.0 parts by mass of polyester resin A was added to a reaction device, and tolylene diisocyanate (manufactured by Mitsui Chemicals, Inc., "Cosmonate (registered trademark) T-80") 13. 9 parts by mass were charged. Next, after raising the external temperature to 80° C., the reaction was continued for 10 hours to synthesize urethane resin A.
The hydroxyl value of the obtained urethane resin was 28.0, the number average molecular weight was 4,010, and the glass transition temperature was -22°C.

[Example 1]
100 parts by mass of an orthocresol type epoxy acrylate resin (manufactured by DIC Corporation, “DICLITE (registered trademark) UE-9000”, nonvolatile content: 63.4% by mass) as an acid-modified vinyl group-containing epoxy resin in a mixing container, Synthesis Example 1 5 parts by mass of the both-end OH group polyester (polyester resin A) obtained in 2., 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (manufactured by BASF Corporation) as a photopolymerization initiator 3.2 parts by mass of "Irgacure (registered trademark) 907"), 1.9 parts by mass of dipentaerythritol hexaacrylate (trademark; "A-DPH" manufactured by Shin-Nakamura Chemical Co., Ltd.) as a polyfunctional acrylate, and a curing agent. 24.4 parts by mass of orthocresol novolac type epoxy resin (manufactured by DIC Corporation, "EPICLON (registered trademark) N-680"), 0.3 part by mass of 2-ethyl-4-methylimidazole as a curing accelerator, organic 13.3 parts by mass of diethylene glycol monoethyl ether acetate was mixed as a solvent and stirred to obtain an epoxy resin composition (X1) of the present invention.
The epoxy resin composition (X1) was applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour.

[Examples 2 to 4 and 6]
Instead of 5 parts by mass of OH group polyester (polyester resin A) at both ends obtained in Synthesis Example 1, 5 parts by mass of both end OH group polyester (polyester resins B and D) obtained in Synthesis Examples 2 and 4 or synthesis Example 1 was repeated except that 5 parts by mass of the both-end COOH group polyester (polyester resin C) obtained in Example 3 or 5 parts by mass of the both-end OH group polyurethane (urethane resin A) obtained in Synthesis Example 5 was used. Similarly, epoxy resin compositions (X2) to (X4) and (X6) were obtained.
The epoxy resin compositions (X2) to (X4) and (X6) were applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour.

[Example 5]
Instead of using 5 parts by mass of the OH group polyester (polyester resin A) at both ends obtained in Synthesis Example 1, 10 parts by mass of the OH group polyester at both ends (polyester resin D) obtained in Synthesis Example 4 is used. An epoxy resin composition (X5) was obtained in the same manner as in Example 1.
The epoxy resin composition (X5) was applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour.

[Comparative Example 1]
In a mixing container, 100 parts by mass of an orthocresol type epoxy acrylate resin (manufactured by DIC Corporation, "DICLITE (registered trademark) UE-9000") as an acid-modified vinyl group-containing epoxy resin (addition of additives of other companies), photopolymerization start 3.2 parts by mass of 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (“Irgacure (registered trademark) 907” manufactured by BASF) as an agent, and dipenta as a polyfunctional acrylate. 1.9 parts by mass of erythritol hexaacrylate ("A-DPH" manufactured by Shin-Nakamura Chemical Co., Ltd.), orthocresol novolac type epoxy resin as a curing agent ("EPICLON (registered trademark) N-680" manufactured by DIC Corporation) Was mixed with 37.7 parts by mass of 2-ethyl-4-methylimidazole as a curing accelerator, and the mixture was stirred until they were mixed to obtain an epoxy resin composition (X′1) of the present invention. ..
The epoxy resin composition (X′1) was applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour.

[Comparative Example 2]
Instead of 5 parts by mass of both-end OH group polyester (polyester resin A) obtained in Synthesis Example 1, polyester resin (manufactured by DIC Corporation, "Polylite (registered trademark) OD-X-2921", number average molecular weight 540, An epoxy resin composition (X′2) was obtained in the same manner as in Example 1 except that 5 parts by mass of a glass transition temperature of −5° C. and a hydroxyl value of 208) were used.
The epoxy resin composition (X′2) was applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour.

[Comparative Example 3]
Instead of 5 parts by mass of the both-end OH group polyester (polyester resin A) obtained in Synthesis Example 1, 5 parts by mass of carboxylic acid-terminated polybutadiene (manufactured by Okamoto Oil Co., Ltd., "SB-20", number average molecular weight 350) was used. An epoxy resin composition (X′3) was obtained in the same manner as in Example 1 except that it was used.
The epoxy resin composition (X′3) was applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour.

[Evaluation method of glass transition temperature (Tg)]
The epoxy resin compositions obtained in Examples and Comparative Examples were applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour. The obtained cured product was cut into a size of width 10 mm×length 50 mm, and the storage elastic modulus (E′) and loss elastic modulus (E″) were measured under the following conditions. E″/E′ was tan δ In the case of, the temperature at which tan δ becomes maximum was taken as the glass transition temperature (Tg, unit: °C), and measurement was performed.
Measuring instrument: Dynamic viscoelasticity measuring instrument (SII Nano Technology Co., Ltd.)
Model: DMA6100
Measurement temperature range: -100°C to 250°C
Temperature rising rate: 5°C/min Frequency: 1 Hz
Measurement mode: Tensile mode Evaluation criteria are as follows.
◯: 135°C or higher Δ: 130°C or higher and lower than 135°C ×: less than 130°C

[Evaluation method of elastic modulus]
The epoxy resin compositions obtained in Examples and Comparative Examples were applied with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour. The obtained cured product was cut into a size of width 10 mm×length 80 mm, and the tensile elastic modulus was measured.
Measuring equipment: Shimadzu Autograph (manufactured by Shimadzu Corporation)
Model: AG-1
Test speed: 10mm/min
Distance between marked lines: 20 mm
The evaluation criteria are as follows.
◯: 1700 MPa or less Δ: Over 1700 MPa, 1800 MPa or less ×: Over 1800 MPa

[Evaluation method of copper foil adhesion]
The epoxy resin compositions obtained in Examples and Comparative Examples were applied on a copper foil with a 50 μm applicator and dried at 80° C. for 30 minutes. It was irradiated with ultraviolet rays of 1000 mJ/cm ² using a metal halide lamp, and was further thermally cured at 160° C. for 1 hour. The obtained cured product was cut into a size of width 10 mm×length 100 mm, and 90° peel strength was measured using a peeling tester.
Measuring equipment: Shimadzu Autograph (manufactured by Shimadzu Corporation)
Model: AG-1
Test speed: 50mm/min
The evaluation criteria are as follows.
○: 0.2N or more △: 0.15N or more and less than 0.2N ×: less than 0.15N

  When the active energy ray-curable compositions of the present invention of Examples 1 to 6 are used, it is possible to produce both a heat resistance and a low elastic modulus, and a cured product having excellent copper foil adhesion. It was

  On the other hand, the composition of Comparative Example 1 did not contain the modified resin (C), and the obtained cured product was inferior in copper foil adhesion and had a high elastic modulus. ..

  The composition of Comparative Example 2 contained a polyester resin having a molecular weight of less than 600, and the obtained cured product had insufficient copper foil adhesion, elastic modulus, and heat resistance.

  The composition of Comparative Example 3 contained a polybutadiene resin having a molecular weight of 350, and the obtained cured product had poor copper foil adhesion.

Claims (9)

An active energy ray-curable composition comprising an acid group-containing epoxy (meth)acrylate resin, an epoxy curing agent and a modifying resin,
The modified resin has at least one selected from the group consisting of a hydroxyl group and a carboxy group,
The glass transition temperature of the modified resin is −100° C. or higher and 50° C. or lower,
The active energy ray-curable composition, wherein the modified resin has a number average molecular weight of 600 or more and 50,000 or less.   The active energy ray-curable composition according to claim 1, wherein the modified resin is at least one selected from the group consisting of a polyester resin and a polyurethane resin.   The active energy ray-curable composition according to claim 1, wherein the functional group value of the specific functional group contained in the modified resin is 2 mgKOH/g or more and 350 mgKOH/g or less.   The content of the modified resin is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the acid group-containing epoxy (meth)acrylate resin. Active energy ray curable composition.   The active energy ray-curable composition according to claim 2, wherein the polyester resin has a bisphenol A skeleton. An epoxy resin modifier,
At least one resin selected from the group consisting of polyester resins and polyurethane resins,
It has at least one specific functional group selected from the group consisting of a hydroxyl group and a carboxy group,
The glass transition temperature is -100°C or higher and 50°C or lower,
An epoxy resin modifier having a number average molecular weight of 600 or more and 50,000 or less.   A solder resist comprising the active energy ray-curable composition according to claim 1.   A dry film comprising the active energy ray-curable composition according to claim 1.   A printed wiring board having a cured product of a resin layer formed from the solder resist according to claim 7.