KR20190070328A - Epoxy resin composition for forming printed wiring board - Google Patents

Abstract

(식 중, R¹ 내지 R³은 각각 독립적으로, 수소원자 또는 메틸기를 나타내고, L¹ 내지 L³은 각각 독립적으로, 탄소원자수 1 내지 10의 알킬렌기를 나타낸다.)

(식 중, L¹ 내지 L³ 및 R¹은 상기와 동일한 의미를 나타내고, X¹ 내지 X³은 각각 독립적으로, 식[2a] 또는 식[2b]로 표시되는 기를 나타내고(단, X¹ 내지 X³ 중 적어도 1개는 식[2b]로 표시되는 기를 나타낸다.), R⁴ 및 R⁵는 각각 독립적으로, 치환되어 있을 수도 있는 탄소원자수 1 내지 20의 알킬기, 또는 치환되어 있을 수도 있는 탄소원자수 6 내지 10의 아릴기를 나타내고, 흑점은 결합수를 나타낸다.)[PROBLEMS] To provide an epoxy resin composition having a low dielectric constant and a low dielectric constant and being suitable for forming a printed wiring board.
[MEANS FOR SOLVING THE PROBLEMS] A mixture comprising (a) an epoxy compound A represented by the formula [1] and a compound B which may have an epoxy group represented by the formula [2], and (b) Epoxy resin composition.

(Wherein R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and L ¹ to L ³ each independently represent an alkylene group having 1 to 10 carbon atoms.)

(Wherein, L ¹ to L ^3, and R ¹ represents the same meaning as defined above, X ¹ to X ³ each independently represents a group represented by the formula [2a] or formula [2b] (stage, X ¹ to And at least one of X ³ represents a group represented by the formula [2b]), R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 20 carbon atoms which may be substituted, or a carbon atom number An aryl group having 6 to 10 carbon atoms, and a black point representing a bond number.

Description

Epoxy resin composition for forming printed wiring board

The present invention relates to an epoxy resin composition for forming a printed wiring board comprising a mixture of epoxy compounds. More particularly, the present invention relates to an epoxy resin composition for obtaining an epoxy resin having a low dielectric constant and a low dielectric constant.

BACKGROUND ART Conventionally, an epoxy resin is an epoxy resin composition which is combined with a curing agent or a curing catalyst. The epoxy resin composition is a high-refractive index layer of an adhesive, an antireflection film (antireflection film for a liquid crystal display or the like), an optical thin film A wiring board, an interlayer insulating film material (an interlayer insulating film material for a build-up printed board, etc.), and the like. Among such electronic materials fields, in applications such as printed wiring boards and interlayer insulating film materials, high adhesion to a substrate, hard coatability, heat resistance, high transparency to visible light, and the like are required.

In these fields, in recent years, in order to process a large amount of data at a high speed, an increase in data transfer amount is required. As a part of this, the increase in the frequency of electric signals is progressing. However, when the high frequency component is increased in the electric signal, the signal waveform is distorted as the delay occurs in the transmission path, the signal intensity is easily attenuated and the loss in the transmission path is increased, , Unnecessary copying in the transmission path is increased, and the like. Accordingly, in order to use the high frequency band, it has become necessary to control the dielectric property of the printed wiring board material (lowering the dielectric constant and reducing the dielectric loss tangent) so as to reduce signal strength loss and signal reflection. However, the conventional epoxy resin generally has a high polarity, and it has been difficult to obtain a sufficient low dielectric constant and low dielectric loss tangent.

As a method for lowering the dielectric constant of an epoxy resin cured product, there has been known a method of lowering the dielectric constant of a cured product by adding hollow particles to the epoxy resin composition and adding an air layer to the cured product obtained from the composition (see, for example, Document 1).

As a method for lowering the dielectric tangent of an epoxy resin cured product, there is known a method of adding a dielectric ceramic powder having a low dielectric loss tangent to an epoxy resin composition (for example, Patent Document 2).

Patent Document 3 discloses that an epoxy resin composition which is liquid or solid and has improved cured properties such as excellent anti-absorption property and mechanical properties can be obtained by modifying triglycidyl isocyanurate as a crystalline epoxy resin .

Japanese Patent Application Laid-Open No. 2010-285624 Japanese Patent Application Laid-Open No. 2004-221572 International Publication No. 2006/035641 pamphlet

However, in the method described in Patent Document 1, since the hollow particles are added to the composition, the optical properties, mechanical properties, thermal properties, and the like of the base resin are changed, which may adversely affect the material design. In the method described in Patent Document 2, the dielectric tangent is lowered, but the relative dielectric constant is increased, so that it is not suitable for use as a printed wiring board. Further, in Patent Document 3, no mention is made regarding the dielectric constant or dielectric tangent of the cured product obtained from the disclosed epoxy resin composition.

An object of the present invention is to provide an epoxy resin composition and a printed wiring board comprising the cured product, which are low dielectric loss tangent and have a low dielectric constant and are suitable for forming a printed wiring board.

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a cured product obtained from an epoxy resin composition comprising a mixture of epoxy compounds having a specific structure exhibits low dielectric loss tangent and low dielectric constant, The present invention has been completed.

Specifically, the present invention provides, as a first aspect, (a) a mixture comprising an epoxy compound A represented by the formula [1] and a compound B which may have an epoxy group represented by the formula [2] An epoxy resin composition for forming a printed wiring board,

[Chemical Formula 1]

(Wherein R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and L ¹ to L ³ each independently represent an alkylene group having 1 to 10 carbon atoms.)

(2)

(Wherein, L ¹ to L ^3, and R ¹ represents the same meaning as defined above, X ¹ to X ³ each independently represents a group represented by the formula [2a] or formula [2b] (stage, X ¹ to And at least one of X ³ represents a group represented by the formula [2b]), R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 20 carbon atoms which may be substituted, or a carbon atom number An aryl group having 6 to 10 carbon atoms, and a black point indicating a bonded number (hand)

As a second aspect, the epoxy resin composition according to the first aspect, wherein L ¹ to L ³ are alkylene groups selected from the group consisting of a methylene group, a trimethylene group and a hexamethylene group,

As a third aspect, the epoxy resin composition according to the first aspect or the second aspect, wherein R ⁴ and R ⁵ are alkyl groups having 1 to 10 carbon atoms which may be substituted,

As a fourth aspect, the epoxy resin composition according to any one of the first to third aspects, wherein R ⁴ and R ⁵ are alkyl groups having 2 to 10 carbon atoms,

As a fifth aspect, the epoxy resin composition according to the first aspect or the second aspect, wherein R ⁴ and R ⁵ are a phenyl group which may be substituted,

As a sixth aspect, the epoxy resin composition according to any one of the first to fifth aspects, which contains 0.2 to 20 moles of the compound B per 1 mole of the epoxy compound A,

In a seventh aspect of the present invention, the curing agent (b) is at least one selected from the group consisting of acid anhydrides, amines, phenol resins, polyamide resins, imidazoles, and polymercaptans. The epoxy resin composition according to any one of

As an eighth aspect, there is provided an epoxy resin composition according to any one of the first to seventh aspects, which comprises 0.5 to 1.5 equivalents of the above-mentioned curing agent (b) based on 1 equivalent of the epoxy group of the epoxy resin (a)

As a ninth aspect, there is provided a printed circuit board comprising a cured product of the epoxy resin composition according to any one of the first to eighth aspects,

.

The epoxy resin composition of the present invention has low dielectric loss tangent and low dielectric constant while having a high glass transition temperature (Tg), and has a low absorption rate.

Therefore, the epoxy resin composition of the present invention can be suitably used as an epoxy resin composition for forming a printed wiring board.

The epoxy resin composition for forming a printed wiring board of the present invention comprises (a) a mixture comprising an epoxy compound A represented by the formula [1] and a compound B which may have an epoxy group represented by the formula [2] .

[Epoxy Compound A represented by the formula [1]

The mixture (a) of the present invention contains the epoxy compound A represented by the above formula [1].

In the formula [1], R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and L ¹ to L ³ each independently represent an alkylene group having 1 to 10 carbon atoms.

Examples of the alkylene group having 1 to 10 carbon atoms represented by L ¹ to L ³ include a methylene group, an ethylene group, a trimethylene group, a 1-methylethylene group, a tetramethylene group, a 1-methyltrimethylene group, , 1-dimethylethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2- Methylpentamethylene group, a 3-methylpentamethylene group, a 1,1-dimethyltetramethylene group, a 1,2-dimethyltetramethylene group, a 1,2-dimethyltetramethylene group, Methyltrimethylene group, a 2,2-dimethyltetramethylene group, a 1-ethyltetramethylene group, a 1,1,2-trimethyltrimethylene group, a 1,2,2-trimethyltrimethylene group, , 1-ethyl-2-methyltrimethylene group, cyclohexane-1,4-diyl group, heptamethylene group, octamethylene group, nonanemethylene group, 2-methyloctamethylene group and decamethylene group have. Preferred are a methylene group, a trimethylene group, and a hexamethylene group.

In the present invention, as the epoxy compound represented by the formula [1], a commercially available epoxy compound may be used, or an epoxy compound containing an isocyanurate ring prepared by a known method may be used. For example, TEPIC (registered trademark) (manufactured by Nissan Chemical Industries, Ltd., triglycidylisocyanurate), tris (3,4-epoxybutyl) isocyanurate, TEIC-VL (5,6-epoxyhexyl) isocyanurate, TEIC-FL (registered trademark) [manufactured by Nissan Chemical Industries, Ltd.], tris Tris (7,8-epoxyoctyl) isocyanurate], and the like can be used.

By using an epoxy compound containing an isocyanurate ring, an epoxy resin excellent in light resistance, weather resistance, heat resistance and transparency can be obtained.

[Compound B represented by the formula [2]

Further, the mixture (a) of the present invention includes the compound B which may have an epoxy group represented by the above formula [2].

In the formula [2], L ¹ to L ³ have the same meanings as defined above, X ¹ to X ³ each independently represent a group represented by the formula [2a] or the formula [2b] ¹ to X ³ represents a group represented by the formula [2b].

In the formula [2a], R ¹ has the same meaning as defined above, and the black point represents the number of bonds.

In the formula [2b], R ¹ and the black point have the same meanings as defined above, R ⁴ and R ^{5 each} represent an alkyl group having 1 to 20 carbon atoms which may be substituted or an alkyl group having 6 to 10 carbon atoms, Lt; / RTI >

Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms represented by R ⁴ and R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, , Straight chain alkyl groups such as a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and an eicosyl group; Isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, sec-isoamyl, isohexyl, Methylhexan-2-yl group, 3-methylhexan-3-yl group, 2,3-dimethylpentane-2 2-ethyl group, 2-ethylhexyl group, octane-2-yl group, 6-methylheptane-2- Methylhexyl group, a nonane-4-yl group, a 2,6-dimethylheptan-3-yl group, a 3,6-dimethylheptan-3-yl group, 3-yl group, a 3,7-dimethyloctyl group, an 8-methylnonyl group, a 3-methylnonan-3-yl group, Ethylnonan-3-yl group, 5-ethylnonan-5-yl group, 2,2,4,5,5-pentamethylhexan-4-yl group, 10-methylundecyl group, Yl group, a tridecan-7-yl group, a 7-ethylundecan-2-yl group, a 3-ethylundecan- Methylpentadecyl group, a 15-methylhexadecyl group, a 4-methylpentadecyl group, a 4-methylpentadecyl group, a 4-methylpentadecyl group, Heptadecan-9-yl group, 3,13-dimethylpentadecan-7-yl group, 2,2,4,8,10,10-hexamethylundecan-5-yl group, Octadecyl group, nonadecan-9-yl group, nonadecan-10-yl group, 2,6,10,14-tetramethylpentadecan-7-yl group and 18- Branched alkyl; Cyclohexyl group, cyclohexyl group, cyclopentyl group, cyclohexyl group, 4-tert-butylcyclohexyl group, 1,6-dimethylcyclohexyl group, menthyl group, cycloheptyl group, cyclooctyl group, bicyclo [2.2. 1] heptan-2-yl group, bonded group, iso-beam group, a 1-adamantyl group, a 2-adamantyl group, a tricyclo [5.2.1.0 ^2,6] decane-4-yl group, tricyclo [5.2.1.0 ^{2 , 6} ] decan-8-yl group, and cyclododecyl group. Is preferably an alkyl group of 1 to 10 carbon atoms, more preferably an alkyl group of 2 to 10 carbon atoms.

These alkyl groups may be substituted with substituents such as cyano group, amino group, nitro group, halogen atom and the like.

Examples of the halogen atom include a fluoro group, a chloro group, a bromo group, and an iodo group.

Examples of the aryl group having 6 to 10 carbon atoms which may be substituted and represented by R ⁴ and R ⁵ include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Preferably, each is a phenyl group.

These aryl groups may be substituted with substituents such as an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group, a cyano group, an amino group, a nitro group and a halogen atom.

In the present invention, as the compound represented by the formula [2], a commercially available epoxy compound may be used, or a compound produced by a known method may be used. For example, a part or all of the epoxy group of the epoxy compound A represented by the formula [1] is reacted with an acid anhydride and substituted with a group represented by the formula [2b] can be preferably used. For example, the compound B is a compound represented by the formula [3] to the epoxy group of the epoxy compound A,

(3)

(1 mole adduct), a compound having two molecules added (2 mole adduct), and a compound having three molecules (one molecule adduct), each of which is represented by the following formula (wherein R ⁴ and R ⁵ have the same meanings as defined above) Is preferably a mixture of the added compound (3-mol adduct).

The acid anhydride represented by the above formula [3] is an acid anhydride obtained from so-called two molecules of monocarboxylic acid, and unlike the acid anhydride obtained from dicarboxylic acid used as a curing agent of the epoxy resin, the function as a curing agent of the epoxy resin is I do not have.

Compound B obtained by reacting an epoxy compound with an acid anhydride has no hydroxyl group, so that even when an unreacted acid anhydride is present, it is not gelated, and storage stability is high.

The acid anhydride is not particularly limited, and examples thereof include acetic anhydride, anhydrous propionic acid, anhydrous butyric acid, anhydrous isobutyric acid, anhydrous acetic anhydride, hexanoic anhydride, anhydrous octanoic acid, trifluoroacetic anhydride, have.

For example, by reacting the epoxy compound A represented by the formula [1] with the acid anhydride represented by the formula [3], an unreacted epoxy compound (epoxy compound A) and an acid anhydride A compound comprising a compound having two molecules of an acid anhydride and a compound having three molecules of an acid anhydride (compound B) can be obtained. The amount of the acid anhydride added compound can be adjusted by adjusting the number of moles of the acid anhydride to be reacted with respect to the number of moles of the epoxy compound A.

The mixture (a) of the present invention is a mixture of epoxy compound A: acid anhydride in a molar ratio of (epoxy group of epoxy compound A) :( acid anhydride) of 1: 0.1 to 1: 1, preferably 1: 0.8. ≪ / RTI >

The reaction product can be obtained by subjecting an unreacted epoxy compound A, a compound obtained by adding one acid anhydride represented by the formula [3] to the epoxy group of the epoxy compound A, a compound obtained by adding two acid anhydrides, The molar ratio of the compound (compound B) can be determined.

The solvent used for the reaction may be inert to the reaction. These solvents include, for example, ketones such as acetone and methyl ethyl ketone; Nitriles such as acetonitrile; Ethers such as tetrahydrofuran and dioxane; Esters such as ethyl acetate; Aromatic hydrocarbons such as chlorobenzene and toluene; And halogenated hydrocarbons such as chloroform and dichloroethane. Or an epoxy compound A such as triglycidylisocyanurate is dissolved by using them alone or as a mixed solvent.

 If necessary, tertiary amines such as triethylamine, tripropylamine and 1,8-diazabicyclo [5.4.0] undecane-7-ene such as triethylamine, ethyltriphenylphosphonium bromide, tetraphenyl Tertiary phosphonium salts such as halogenated monoalkyltriphenylphosphonium represented by phosphonium bromide and the like, imidazole-based compounds such as 2-ethyl-4-methylimidazole, quaternary ammonium salts such as tetraethylammonium bromide, Phosphorus compounds such as triphenylphosphine and the like can be used.

The reaction temperature is, for example, carried out at the reflux temperature of the solvent, until the epoxy group content titrated with a 0.1 N perchloric acid / acetic acid solution reaches a theoretical value (value at which the added acid anhydride disappears by reaction) Is done. After completion of the reaction, the solvent may be distilled off to obtain a mixture (a).

< (a) Mixture >

In the mixture of the present invention, the content of the epoxy compound A represented by the formula [1] and the compound B represented by the formula [2] is not particularly limited. For example, B of 0.2 to 20 mol, preferably 0.7 to 4 mol.

It is preferable that the total sum of the epoxy group of the compound A and the epoxy group of the compound B is 2 or more on average in terms of one molecule (the total epoxy group number is divided by the total number of molecules). If the number is less than 2, the physical properties of the cured product, particularly the heat resistance, are undesirably low.

The mixture of the present invention can be used in combination with the epoxy compound A represented by the formula [1] and the compound B represented by the formula [2] within the range not impairing the effect of the present invention have.

The epoxy compound A represented by the above formula [1], the compound B represented by the formula [2] and other epoxy compounds are used in a molar ratio of epoxy groups, for example, in the range of 1: 0 to 1:20 It is possible.

As the other epoxy compounds, various polyfunctional epoxy compounds which are commercially available can be used without particular limitation.

Examples of the epoxy compound usable in the present invention include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly ) Propylene glycol diglycidyl ether, trimethylol ethane triglycidyl ether, trimethylol propane triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl ), Cyclohexane, glycerol triglycidyl ether, diglycerol polydiglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris (4-glycidyloxyphenyl ) Propane, diglycidyl 1,2-cyclohexanedicarboxylate, 4,4'-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexanecarboxylic acid 3 ', 4'- Epoxycyclohexylmethyl, triglycidyl-p-aminophenol, tetraglycidyl methadienyldiamine, tetraglycidyldiaminodiphenylmethane, tetra Bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, penta But are not limited to, erythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, diglycidyl phthalate, diglycidyl tetrahydrophthalate, neopentyl glycol diglycidyl ether, (2-glycidyloxyethyl) isocyanurate, monoallyldiglycidylisocyanurate, N, N'-diglycidyl (meth) acrylate, N, N'-bis (2,3-dipropionyloxypropyl) N "-glycidylisocyanurate, tris (2, , 2-bis (glycidyloxymethyl) butyl) 3,3 ', 3 "- (2,4,6-trioxo -1,3,5-triazine-1,3,5-triyl) tripropanoate, sorbitol polyglycidyl ether, diglycidyl adipate, diglycidyl o-phthalate, dibromophenyl Glycidyl ether, 1,2,7,8-diepoxy octane, 1,6-dimethylol perfluorohexane diglycidyl ether, 4- (spiro [3,4-epoxycyclohexane- - [1,3] dioxane] -2'-yl) -1,2-epoxycyclohexane, 1,2-bis (3,4-epoxycyclohexylmethoxy) Methyl cyclohexane carboxylic acid 4 ', 5'-epoxy-2'-methylcyclohexylmethyl, ethylene glycol bis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate , Bis (2,3-epoxycyclopentyl) ether, and the like, but are not limited thereto.

These epoxy compounds may be used alone or as a mixture of two or more thereof.

As an example of the above epoxy compound, the following commercially available products can be mentioned.

As the liquid epoxy compound, TEPIC (registered trademark) -UC (manufactured by Nissan Chemical Industries, Ltd.), jER (registered trademark) 828 and copper (registered trademark) YX8000 (all manufactured by Mitsubishi Chemical Corporation) ) DME100 (manufactured by Shin-Nihon Rika K.K.), and Celloxide 2021P (manufactured by Daicel Co., Ltd.).

<(b) Curing agent>

The epoxy resin composition for forming a printed wiring board of the present invention comprises (c) a curing agent.

The curing agent is not particularly limited, but for example, an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, a polymercaptan, or a mixture thereof can be used. Of these, acid anhydrides and amines are particularly preferred. These curing agents can be used by dissolving them in a solvent even if they are solid. However, since the density of the cured product is lowered due to the evaporation of the solvent, and the strength is lowered and the water resistance is lowered due to the formation of the pores, it is preferable that the curing agent itself is liquid at room temperature and normal pressure.

The curing agent may be contained in an amount of 0.5 to 1.5 equivalents, preferably 0.8 to 1.2 equivalents based on 1 equivalent of the epoxy group of the epoxy compound. The equivalence of the curing agent with respect to the epoxy compound is represented by the equivalence ratio of the curing agent of the curing agent to the epoxy group. On the other hand, when the mixture (a) containing the epoxy compound represented by the above formula [1] and the compound represented by the formula [2] is used in combination with other epoxy compounds, the equivalent of these epoxy compounds to the epoxy group Is in the above range.

The acid anhydride is preferably an anhydride of a compound having a plurality of carboxyl groups in one molecule. Examples of these acid anhydrides include acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tris trimellitate, maleic anhydride, tetrahydroanhydride Phthalic acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylmixhistronic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, chlorendic anhydride, and the like.

Among these, methyltetrahydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride (methylnadic anhydride, methylmaleic anhydride), methylnadic anhydride, Hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecenyl myristoic acid, methylhexahydrophthalic anhydride, and mixtures of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride. These liquid acid anhydrides have a viscosity of about 10 to 1,000 mPa · s as measured at 25 ° C. In the acid anhydride group, one acid anhydride group is calculated as one equivalent.

Examples of the amine include piperidine, N, N'-dimethylpiperazine, triethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, 2- (dimethylaminomethyl) But are not limited to, phenol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, di (1-methyl-2-aminocyclohexyl) methane, mentantiamine, isophoronediamine , Diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, xylene diamine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Among them, preferred are the liquid phase diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, bis (1-methyl-2-aminocyclohexyl) methane, mentantiamine, Isophoronediamine, diaminodicyclohexylmethane and the like can be preferably used.

Examples of the phenol resin include a phenol novolac resin and a cresol novolak resin.

The polyamide resin is a polyamide amine produced by condensation of a dimer acid and a polyamine and having a primary amine and a secondary amine in the molecule.

The imidazoles include, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, And the like.

As the polymercaptan, for example, a mercaptan group is present at the end of the polypropylene glycol chain, or a mercaptan group is present at the end of the polyethylene glycol chain, and is preferably in a liquid state.

<Curing accelerator>

When a cured product is obtained from the epoxy resin composition for forming a printed wiring board of the present invention, a curing accelerator (also referred to as a curing aid) may be used in addition to the curing agent as appropriate.

Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine and tributylphosphine; Quaternary phosphonium salts such as ethyltriphenylphosphonium bromide, tetrabutylphosphonium O, and O-diethylphosphorodithioate; Diazabicyclo [5.4.0] undeca-7-ene, 1,8-diazabicyclo [5.4.0] undeca-7-ene and octylic acid, zinc octylate, tetrabutylammonium And quaternary ammonium salts such as bromide. Further, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole mentioned as the above-mentioned curing agents, 2,4,6-tris (dimethylaminomethyl) phenol and benzyldimethylamine Amines can also be used as curing accelerators for other types of curing agents.

These curing accelerators can be used in a proportion of 0.001 to 0.1 part by mass based on 1 part by mass of the curing agent.

<< Epoxy resin composition for forming printed wiring board >>

In the present invention, an epoxy resin composition for forming a printed wiring board is obtained by mixing the epoxy compound A represented by the formula [1] and the compound B represented by the formula [2], the curing agent and, if necessary, a curing accelerator . These mixtures are preferably mixed with stirring under reduced pressure and defoamed.

The cured product obtained from the epoxy resin composition can be obtained by applying the epoxy resin composition to a substrate or pouring it into a mold plate coated with a release agent and preliminarily curing the composition at a temperature of, for example, 100 to 120 ° C, (Post-curing). The cured product obtained from the epoxy resin composition of the present invention can be suitably used for a printed wiring board.

The heating time can be appropriately adjusted according to the size or thickness of the epoxy resin. For example, for example, the pre-curing and final curing are each 1 to 12 hours, for example 2 to 5 hours.

Examples of the method of applying the epoxy resin composition of the present invention on a substrate include a coating method such as a flow coating method, a spin coating method, a spray coating method, a screen printing method, a flexo printing method, an inkjet printing method, A curtain coating method, a roll coating method, a gravure coating method, a dipping method, and a slit method.

<(c) Curing catalyst>

In the present invention, a curing catalyst, for example, (c1) an acid generator and / or (c2) a base generator may be used. Thus, even when the epoxy compound of the present invention is mixed with the curing catalyst, hardening does not occur immediately, so that the storage stability is excellent and a sufficient working time is obtained.

[(c1) acid generator]

(c1) As the acid generator, a photo acid generator or a thermal acid generator may be used. The photoacid generator or thermal acid generator is not particularly limited as long as it generates an acid (Lewis acid or Bronsted acid) directly or indirectly by light irradiation or heating. The epoxy resin composition containing the thermal acid generator can be cured in a short time by heating. Further, the epoxy resin composition containing the photoacid generator is cured by light irradiation, not by heating, so that it can be used on substrates and parts having low heat resistance.

Specific examples of the photoacid generator include an onium salt such as an iodonium salt, a sulfonium salt, a phosphonium salt and a selenium salt, a metallocene complex compound, an iron arene complex compound, a disulfone compound, a sulfonic acid derivative compound, Acetophenone derivative compounds, and diazomethane-based compounds.

Examples of the iodonium salt include diphenyliodonium, 4,4'-dichlorodiphenyliodonium, 4,4'-dimethoxydiphenyliodonium, 4,4'-di-tert-butyldiphenyl Iodonium, 4-methylphenyl (4- (2-methylpropyl) phenyl) iodonium, 3,3'-dinitrophenyl iodonium, 4- (1-ethoxycarbonylethoxy) Bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenylsulfonium iodide) such as iodonium, such as iodonium, Di (phenyl) borate, diaryliodonium salts such as hexafluorophosphate, hexafluoroarsenate and hexafluoroantimonate, and the like.

Examples of the sulfonium salt include triphenylsulfonium, diphenyl (4-tert-butylphenyl) sulfonium, tris (4-tert- butylphenyl) sulfonium, diphenyl (4-methoxyphenyl) sulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) - (phenylthio) phenyl) sulfonium, etc., chloride, bromide, trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, etc. And the like.

Examples of the phosphonium salt include tetraphenylphosphonium, ethyltriphenylphosphonium, tetra (p-methoxyphenyl) phosphonium, ethyltri (p-methoxyphenyl) phosphonium, benzyltriphenylphosphonium And aryl phosphonium salts such as chloride, bromide, tetrafluoroborate, hexafluorophosphate, and hexafluoroantimonate, and the like.

Examples of the selenium salt include triarylselenium salts such as triphenylselenium hexafluorophosphate and the like.

Examples of the iron arene complex compound include bis (η ⁵ -cyclopentadienyl) (η ⁶ -isopropylbenzene) iron (II) hexafluorophosphate and the like.

These photoacid generators may be used alone or in combination of two or more.

Examples of the thermal acid generator include a sulfonium salt and a phosphonium salt, and a sulfonium salt is preferably used.

Examples of these exemplified compounds include the compounds mentioned as examples of various onium salts in the above-described photoacid generator.

These thermal acid generators may be used alone or in combination of two or more.

Among these, as the acid generator (c1), a sulfonium salt compound or an iodonium salt compound is preferable, and for example, a compound having an anionic species such as hexafluorophosphate or hexafluoroantimonate exhibiting strong acidity is preferable.

The content of the acid generator (c1) in the epoxy resin composition of the present invention is 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the epoxy compound (a) Mass part. On the other hand, when the epoxy compound represented by the above formula [1] and other epoxy compounds are used in combination, the content with respect to 100 parts by mass of the total epoxy compound is within the above range.

[(c2) Base generator]

As the (c2) base generator, a photo-base generator or a thermal base generator can be used. The photo-acid generator or the thermal base generator is not particularly limited as long as it generates a base (Lewis base or Bronsted base) directly or indirectly by light irradiation or heating. The epoxy resin composition containing the thermal base generator can be cured in a short time by heating. Further, the epoxy resin composition containing the photo-base generator is cured by light irradiation without heating, so that it can be used for substrates and parts having low heat resistance.

Examples of the photobase generators include alkylamine-based photobase generators such as 9-anthrylmethyl = N, N-diethylcarbamate; Dicyclohexylcarbamate, dicyclohexylcarbamate, dicyclohexylcarbamate, dicyclohexylcarbamate, 1- (9,10-anthraquinone-2-yl) ethyl N, N- (9,10-anthraquinone-2-yl) ethyl = N-cyclohexylcarbamate, cyclohexylammonium = 2- ( 3-benzoylphenyl) propionate, and (E) -N-cyclohexyl-3- (2-hydroxyphenyl) acrylamide; (E) -1-piperidino-3- (2-hydroxyphenyl) -2-propen-1-one, (2-nitrophenyl ), A piperidine-based photobase such as methyl = 4-hydroxypiperidine-1-carboxylate and (2-nitrophenyl) methyl = 4- (methacryloyloxy) piperidine- Generator; 2-diisopropyl-3- (bis (dimethylamino) methylene) guanidinium = 2- (3-benzoylphenyl) propionate, Tetrabutyl triphenylborate, 1,5,7-triazabicyclo [4.4.0] deca-5-ene Guanidine-based photobase generators such as 2- (9-oxoxanthen-2-yl) propionate; And imidazole-based photoacid generators such as 1- (9,10-anthraquinon-2-yl) ethyl imidazole-1-carboxylate.

These photobase generators may be used singly or in combination of two or more.

Photobase generators are available as commercial products. For example, the photobase generator WPBG series (WPBG-018, Dong 027, Dong 022, Dong 140, Dong 266, Dong 300) manufactured by Wako Pure Chemical Industries, Etc.) and the like.

Examples of the thermal base generator include carbamates such as 1-methyl-1- (4-biphenyl) ethyl carbamate and 2-cyano-1,1-dimethyl ethyl carbamate; Urea, and N, N-dimethyl-N'-methylene; Guanidines such as guanidine trichloroacetate, guanidine phenylsulfonylacetate and guanidine phenylpropionate; Dihydropyridines such as 1,4-dihydronickotinamide; N- (isopropoxycarbonyl) -2,6-dimethylpiperidine, N- (tert-butoxycarbonyl) -2,6-dimethylpiperidine, N- (benzyloxycarbonyl) Dimethylpiperidines such as 6-dimethylpiperidine; Quaternary ammonium salts such as tetramethylammonium phenylsulfonylacetate and tetramethylammonium phenylpropionate; Dicyandiamide, and the like. Further, U-CAT (registered trademark) SA810, SA831, SA841, SA851 (which are described above), which are salts of 1,8-diazabicyclo [5.4.0] undeca- ), And the like.

These thermal base generators may be used singly or in combination of two or more.

The content of the base generator (c2) in the epoxy resin composition of the present invention is 0.1 to 20 parts by mass, or 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the epoxy compound (a) Mass part. On the other hand, when the mixture (a) containing the epoxy compound represented by the formula [1] and the compound represented by the formula [2] is used in combination with other epoxy compounds, The content falls within the above range.

In the present invention, an epoxy resin composition is obtained by mixing the mixture (a) with the curing catalyst. The operating conditions of the mixing for obtaining the epoxy resin composition are as described above.

In the present invention, an epoxy resin composition comprising the above mixture (a) and a photoacid generator or a photoacid generating agent can be coated on a substrate and cured by light irradiation. It may also be heated before or after light irradiation.

Further, in the present invention, the epoxy resin composition containing the mixture (a) and the thermal acid generator or the heat base generator may be coated on the substrate and cured by heating.

Furthermore, the epoxy resin composition containing the mixture (a), the thermal acid generator, and the photoacid generator or the heat base generator and the photo base generator may be coated on the substrate and cured by heating after heating.

The thickness of the coating film formed from the epoxy resin composition of the present invention can be selected from the range of about 0.01 to 10 mm depending on the use of the cured product. For example, when used for a photoresist, the thickness of the coating film is preferably 0.05 to 10 m (Particularly, 100 m to 1 mm) when used for a printed wiring board, and 0.1 to 100 m (particularly 0.3 to 50 m) when used for an optical thin film.

Examples of the light to be irradiated or exposed in the case of using the photoacid generator or the photoacid generating agent include gamma rays, X-rays, ultraviolet rays, visible rays and the like, and usually visible rays or ultraviolet rays, .

The wavelength of the light is, for example, 150 to 800 nm, preferably 150 to 600 nm, more preferably 200 to 400 nm, particularly 300 to 400 nm.

The irradiation light amount differs depending on the thickness of the coating film, and can be, for example, about 2 to 20,000 mJ / cm ² , and preferably about 5 to 5,000 mJ / cm ² .

The light source can be selected according to the kind of light to be exposed. For example, in the case of ultraviolet light, a low pressure mercury lamp, a high pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a halogen lamp, Laser, etc.), UV-LED, and the like. By such light irradiation, the curing reaction of the composition proceeds.

The heating of the coating film, which is carried out if necessary after the light irradiation, using a thermal acid generator or a thermal base generator, or a photoacid generator or a photoacid generator, is carried out at room temperature (about 23 ° C) to 250 ° C Lt; / RTI &gt; The heating time can be selected in the range of 3 seconds or more (for example, about 3 seconds to 5 hours), for example, about 5 seconds to 2 hours.

Furthermore, in the case of forming a pattern or an image (for example, in the case of producing a printed wiring board or the like), a coated film formed on a substrate may be pattern-exposed. This pattern exposure can be performed by scanning of laser light or by irradiating light through a photomask. A pattern or an image can be formed by developing (or dissolving) the non-irradiated area (unexposed area) generated by such pattern exposure with a developing solution.

As the developing solution, an aqueous alkali solution or an organic solvent can be used.

Examples of the aqueous alkali solution include aqueous solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; An aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide or choline; And amine aqueous solutions such as ethanolamine, propylamine and ethylenediamine.

The alkali developing solution is generally an aqueous solution of 10 mass% or less, preferably 0.1 to 3 mass%, or the like. Furthermore, alcohol or a surfactant may be added to the developer, and the amount thereof added is preferably 0.05 to 10 parts by mass based on 100 parts by mass of the developer. Specifically, 0.1 to 2.38 mass% aqueous solution of tetramethylammonium hydroxide can be used.

As the organic solvent as the developing solution, general organic solvents can be used, and for example, aromatic hydrocarbons such as toluene; Esters such as ethyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate; Amides such as N, N-dimethylformamide (DMF); Nitriles such as acetonitrile; Ketones such as acetone and cyclohexanone; And alcohols such as methanol, ethanol, 2-propanol, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether. These may be used alone or as a mixture of two or more kinds.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and the like can be preferably used.

<Solvent>

The above-mentioned epoxy resin composition may contain a solvent as required.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; Esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate; Hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionate, 3- hydroxypropionate, 3- hydroxypropionate, 3- Hydroxypropyl hydroxypropionate, butyl hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and methyl 2-hydroxy-3-methylbutanoate; Methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methylpropoxyacetate, Propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, propoxyacetic acid, butoxyacetic acid, butoxyacetic acid, butoxyacetic acid, Ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Propyl methoxy propionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, Propoxy propionate, propyl 3-butoxy propionate, butyl 3-butoxy propionate, methyl cellosolve acetate, ethyl 3-ethoxypropionate, (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether Propionate, propylene glycol monopropyl ether propionate, propylene glycol Ether esters such as recall monobutyl ether propionate, and the like; Ketones such as methyl ethyl ketone (MEK), 4-hydroxy-4-methyl-2-pentanone, and cyclohexanone; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol mono Alcohols such as butyl ether; And ethers such as tetrahydrofuran (THF), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like.

<Other Curable Monomers>

In the present invention, a vinyl group-containing compound, an oxetanyl group-containing compound and the like can be used as the cation-setting monomer for the purpose of adjusting the viscosity of the epoxy resin composition and improving the curability.

The vinyl group-containing compound is not particularly limited as long as it is a compound having a vinyl group, and examples thereof include 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl ether (DEGV), 2- HBVE), triethylene glycol divinyl ether, and other vinyl ether compounds. A vinyl compound having a substituent such as an alkyl group or an allyl group at the? -Position and / or? -Position can also be used. Further, a vinyl ether compound containing a cyclic ether group such as an epoxy group and / or an oxetanyl group can be used, and examples thereof include oxynorbornenedivinyl ether and 3,3-dimethanoloxetane divinyl ether .

Further, a compound having a vinyl group and a (meth) acrylic group can be used, and for example, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate and the like can be given.

These vinyl group-containing compounds may be used alone or in combination of two or more.

The oxetanyl group-containing compound is not particularly limited as long as it is a compound having an oxetanyl group, and examples thereof include 3-ethyl-3- (hydroxymethyl) oxetane (OXA), 3- (POX), bis ((3-ethyl-3-oxetanyl) methyl) ether (DOX), 1,4- Ethylhexyloxy methyl) oxetane (EHOX), 3-ethyl-3 - ((3-triethoxysilylpropoxy) methyl) oxetane (TESOX), oxetanyl And oxetane compounds such as sesquioxane (OX-SQ) and phenol novolak oxetane (PNOX-1009).

Further, a compound having an oxetanyl group and a (meth) acryl group can be used, and for example, (meth) acrylate (3-ethyl-3-oxetanyl) methyl and the like can be given.

These oxetanyl group-containing compounds may be used alone or in combination of two or more.

<Other ingredients>

The above-mentioned composition may contain additives for general use as required. Examples of such an additive include additives such as a thickener, a sensitizer, a defoaming agent, a leveling agent, a coating improver, a lubricant, a stabilizer (an antioxidant, a heat stabilizer, a light stabilizer and the like), a plasticizer, a surfactant, , A curing agent and the like. These additives may be used alone or in combination of two or more.

To the epoxy resin composition of the present invention, a surfactant may be added for the purpose of improving coatability. Such a surfactant includes, but is not limited to, a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent. These surfactants may be used alone or in combination of two or more.

Among these surfactants, a fluorine-based surfactant is preferable from the viewpoint of the improvement of the coating property. Specific examples of the fluorochemical surfactant include, for example, EF-top (registered trademark) EF-301, EF-303 and EF-352 (all manufactured by Mitsubishi Materials Electronics Co., Ltd.) F-171, F-173, F-482, R-08, R-30, R-90 and BL-20 all manufactured by DIC Co., Fluorad FC- S-382, SC-101, SC-102, and SC-102 (manufactured by Asahi Glass Co., Ltd.) 103, SC-104, SC-105 and SC-106 [all manufactured by AGC Seiyam Chemical Co., Ltd.], and the like.

The addition amount of the surfactant in the epoxy resin composition of the present invention is 0.01 to 5% by mass, preferably 0.01 to 3% by mass, more preferably 0.01 to 2% by mass based on the solid content of the epoxy resin composition %to be.

To the epoxy resin composition of the present invention, an adhesion promoter may be added for the purpose of improving adhesion with the substrate after development. Examples of the adhesion promoter include chlorotrimethylsilane, trichloro (vinyl) silane, chloro (dimethyl) (vinyl) silane, chloro (methyl) (diphenyl) silane, chloro (chloromethyl) Chlorosilanes; (Meth) acrylates such as methoxytrimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, ethoxy (dimethyl) (vinyl) silane, dimethoxydiphenylsilane, triethoxy (Meth) acryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, trimethoxy (3- (N-piperidinyl) propyl) silane Alkoxy silane; Silane residues such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyl (trimethylsilyl) amine and trimethylsilylimidazole; There may be mentioned imidazole, indazole, benzimidazole, benzotriazole, methacryloimidazole, methacrylopyrimidine 2-mercaptobenzoimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole, Nitrogen-containing heterocyclic compounds such as thiouracil and the like; 1,1-dimethylurea, and 1,3-dimethylurea, and thioureas. These adhesion promoters may be used alone or in combination of two or more.

The amount of the adhesion promoter to be added to the epoxy resin composition of the present invention is usually 20 mass% or less, preferably 0.01 to 10 mass%, more preferably 0.05 to 5 mass%, based on the solid content of the epoxy resin composition %to be.

The epoxy resin composition of the present invention may contain a sensitizer. Examples of usable sensitizers include anthracene, phenothiazine, perylene, thioxanthone and benzophenanthioxanthone. Further, as the sensitizing dye, there may be mentioned thiopyrylium salt dye, merocyanine dye, quinoline dye, styrylquinoline dye, ketokmarine dye, thioxanthene dye, xanthene dye, oxolin dye, cyanine dye A chromatic dye, a rhodamine dye, and a pyruvium salt dye. Particularly preferred is an anthracene-based sensitizer which, when used in combination with a cationic curing catalyst (radiation-sensitive cationic polymerization initiator), has dramatically improved sensitivity and also has a radical polymerization initiating function. For example, a cationic curing system and a radical In the case of employing a hybrid type in which a curing system is used in combination, the catalyst species can be simplified. Specific examples of the anthracene compound include dibutoxyanthracene, dipropoxyanthraquinone, and the like.

Examples of the sensitizer when a base generator is used as a curing catalyst include acetophenones, benzoins, benzophenones, anthraquinones, xanthones, thioxanthones, ketals, tertiary amines, etc. .

The amount of the sensitizer added to the epoxy resin composition of the present invention is 0.01 to 20% by mass, preferably 0.01 to 10% by mass, based on the solid content of the epoxy resin composition.

Industrial availability

The epoxy resin composition comprising the mixture (a) and the curing agent (b) of the present invention has a light and a thermosetting property, and can be used as a high refractive index layer, an optical thin film (reflector, etc.) of an adhesive, an antireflection film (antireflection film for liquid crystal display, , A sealing material for electronic parts, a printed wiring board, an interlayer insulating film material (an interlayer insulating film material for a build-up printed board, etc.). In particular, it can be widely used as an electronic material requiring low dielectric constant and low dielectric constant such as a printed wiring board and an interlayer insulating film material.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

On the other hand, in the examples, the apparatus and conditions used for preparation of the sample and analysis of the physical properties are as follows.

(1) Gas Chromatography (GC)

Device: GC-2010 Plus made by Shimazu Works Co., Ltd.

Detector: FID

Column: Agilent J & W GC column HP-5 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies,

Injection amount: 1.0 μL

Inlet temperature: 250 ° C

Column temperature: 40 DEG C (for 5 minutes), temperature rise to 300 DEG C at 20 DEG C / min, 300 DEG C (for 12 minutes)

(2) High Performance Liquid Chromatography (HPLC)

Device: Agilent Technologies 1200 Infinity LC System

Detector: UV (205 nm)

Column temperature: 40 ° C

Column: Inertsil (registered trademark) ODS-4 (particle size: 5 m, inner diameter: 4.6 mm, length: 250 mm)

Injection volume: 10 μL

Mobile phase Composition: Acetonitrile / pure water (volume ratio) = 4/96 to 90/10 (linear gradient, 30 minutes)

Flow rate: 1.5 mL / min

(3) Gel permeation chromatography (GPC)

Device: HLC-8220GPC manufactured by Tosoh Corporation

Column: Shodex (registered trademark) GPC KF-804L, KF-805L manufactured by Showa Denko K.K.

Column temperature: 40 ° C

Eluent: tetrahydrofuran

Detector: RI

(4) Epoxy equivalent

Apparatus: Potentiometric automatic titrator AT-510 made by Kyoto Electronics Co., Ltd.

(5) dielectric tangent, relative dielectric constant

Device: Key Site Technologies E4980A Fresh LCR meter

Sample holder: room temperature sample holder 12962 manufactured by Toyo Technica Co., Ltd.

(6) Glass transition temperature Tg

Device: Dynamic viscoelasticity measurement device (DMA) manufactured by TA Instrument Q800

Deformation mode: Dual cantilever

Frequency: 1Hz

Distortion: 0.05%

Sweep temperature: 30 to 300 ℃

Heating rate: 5 ° C / min

(7) Flexural modulus, flexure

Apparatus: Table top type precision universal testing machine made by Shimazu Kogyo Co., Ltd. Autograph AGS-5kNX

(8) Ovens

Device: Yamato Scientific Co., Ltd. Ventilation low temperature thermostat DNF400

In addition, the weak symbols indicate the following meanings.

BA: anhydrous butyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

BzA: Anhydrous benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

iBA: anhydrous isobutyric acid (manufactured by Tokyo Chemical Industry Co., Ltd.)

OA: anhydrous calcium carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.)

PA: anhydrous propionic acid [Daicel APA Co., Ltd.]

P3EPB: ethyltriphenylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.)

P4PB: tetraphenylphosphonium bromide (manufactured by TOKYO HOSAGO CO., LTD.)

BPA: Bisphenol A type epoxy resin [jER (registered trademark) 828, Mitsubishi Chemical Corporation)

TGIC: triglycidylisocyanurate [TEPIC (registered trademark) -S manufactured by Nissan Chemical Industries, Ltd.]

MH700: a mixture of 4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride (molar ratio 70:30) (Rikacid (registered trademark) MH-700 manufactured by Shin-Nippon Rika KK)

PX4ET: tetrabutylphosphonium O, O-diethylphosphorothioate (Hishikolin (registered trademark) PX-4ET manufactured by Japan Chemical Industry Co., Ltd.)

[Production Example 1] Production of TGIC anhydrous propionic acid-modified product (PA-TGIC)

To the reaction flask were added 60.0 g (202 mmol) of TGIC and 54 g of toluene. This mixture was refluxed, and a mixture of 21.2 g (162 mmol) of PA and 0.06 g (0.156 mmol) of P3EPB was added dropwise. After completion of dropwise addition, reflux was carried out for 2 hours. Toluene was distilled off under reduced pressure from the reaction mixture to obtain TGIC anhydrous propionic acid modified product (PA-TGIC) as a liquid product. The epoxy equivalent of the obtained PA-TGIC measured according to JIS K7236: 2009 was 181 (theoretical value 182). The TGIC (non-adduct): 1 mole adduct: 2 moles adduct: 3 moles adduct (area ratio) in the HPLC analysis was 33: 45: 19: 3.

[Preparation Example 2] Preparation of TGIC anhydrous butyric acid modified product (BA-TGIC)

To the reaction flask, 40.0 g (135 mmol) of TGIC and 14 g of acetonitrile were added. While refluxing the mixture, a mixture of 17.0 g (108 mmol) of BA, 0.026 g (0.062 mmol) of P4PB and 0.4 g of acetonitrile was added dropwise. After completion of dropwise addition, reflux was performed for 24 hours. The acetonitrile was distilled off under reduced pressure from the reaction mixture to obtain TGIC anhydrous butyric acid modified product (BA-TGIC) as a liquid product. The epoxy equivalent of the obtained BA-TGIC was 192 (theoretical value 193). In addition, in the HPLC analysis, the adduct (area ratio) of TGIC (non-adduct): 1 mole adduct: 2 moles adduct: 3 moles was 33: 52: 14: 0.1.

[Preparation Example 3] Preparation of TGIC anhydrous isobutyric acid modified product (iBA-TGIC)

By operating in the same manner as in Production Example 2 except that BA was changed to iBA, TGIC anhydrous isobutyric acid modified product (iBA-TGIC) was obtained as a liquid product. The epoxy equivalent of the obtained iBA-TGIC was 192 (theoretical value 193). The TGIC (non-adduct): 1 mole adduct: 2 moles adduct: 3 moles adduct (area ratio) in the HPLC analysis was 30: 52: 17: 1.

[Production Example 4] Production of TGIC anhydrous calcium carbonate modified product (OA-TGIC)

(OA-TGIC) was obtained as a liquid product by operating in the same manner as in Production Example 2 except that BA was changed to 29.1 g (108 mmol) of OA. The epoxy equivalent of the obtained OA-TGIC was 234 (theoretical value 234). The TGIC (non-adduct): 1 mole adduct: 2 moles adduct: 3 moles adduct (area ratio) in the HPLC analysis was 29: 43: 24: 4.

[Preparation Example 5] Preparation of TGIC anhydrous benzoic acid modified product (BzA-TGIC)

TGIC anhydrous benzoic acid (BzA-TGIC) was obtained as a liquid product by operating in the same manner as in Production Example 2 except that BA was replaced by 24.4 g (108 mmol) of BzA. The epoxy equivalent of the obtained BzA-TGIC was 217 (theoretical value 217). The TGIC (non-adduct): 1 mole adduct: 2 moles adduct: 3 moles adduct (area ratio) in the HPLC analysis was 15: 43: 35: 7.

[Examples 1 to 5, Comparative Examples 1 to 2]

To 100 parts by mass of the epoxy compound shown in Table 1, MH700 as a curing agent was added in an equimolar amount to the epoxy group of the epoxy compound and 1 part by mass of PX4ET as a curing accelerator. The mixture was stirred under reduced pressure at room temperature (about 23 ° C) for 30 minutes to be defoamed to prepare an epoxy resin composition.

Each composition was sandwiched between two glass substrates, each of which had been subjected to a releasing treatment in advance with OPTUL (registered trademark) DSX (manufactured by Daikin Industries, Ltd.) together with a spacer made of a K-shaped silicone rubber having a thickness of 3 mm. This was heated (pre-curing) in an oven at 100 캜 for 2 hours, then heated to 150 캜 and heated (final curing) for 5 hours. After cooling, the glass substrate was removed to obtain each cured product having a thickness of 3 mm.

Dielectric tangent, relative dielectric constant, glass transition temperature, water absorption, bending elastic modulus, and warpage of the obtained cured product were evaluated. On the other hand, each physical property value was measured by the following procedure. The results are shown together in Table 1.

[Dielectric tangent]

The dielectric loss tangent when a voltage of 1 V and 1 MHz was applied to the test piece sandwiched between the electrodes of the holder was measured.

[Relative dielectric constant]

The capacitance Cp when a voltage of 1 V and 1 MHz was applied to the test piece sandwiched between the electrodes of the holder was measured and divided by the capacitance C ₀ of air measured under the same conditions.

[Glass transition temperature (Tg)]

The storage elastic modulus E 'and the loss elastic modulus E "were measured by DMA, and the temperature at which the value of tan? (Loss elastic modulus E" / storage elastic modulus E') obtained from these was the maximum was defined as Tg.

[Absorption Rate]

Measured according to JIS K-6911: 2006. Specifically, as a pretreatment, a test piece (30 × 30 × 3 mm) was dried in a glass container kept at 50 ° C. in an oil bath for 24 hours. Cooling the specimen to 20 ℃ in a desiccator, which was then measured for the weight (W ₁ [g]). Next, the test piece was immersed in distilled water of boiling water for 100 hours, taken out, cooled in oily water at 20 캜 for 30 minutes to wipe the water, and the mass (W ₂ [g]) immediately after the absorption was measured. From these values, the absorption rate was calculated by the following equation.

Absorption rate [%] = (W ₂ -W ₁ ) / W ₁ 100

[Bending modulus of elasticity]

Measured according to JIS K-6911: 2006. Specifically, a load was applied to the center of a test piece (80 × 10 × 3 mm) supported at a distance of 64 mm between points by a pressurized wedge, and the gradient F / Y [N / mm] of the straight portion of the load-deflection curve was obtained. The bending elastic modulus was calculated from this and the values of the distance L [mm] between the points, the width W [mm] of the test piece, and the thickness h [mm].

Flexural modulus ^{[MPa] = (L 3 ÷} 4Wh 3) × (F / Y)

[warp]

Bending of the breaking point (indentation distance). > 30 drops before breaking.

[Table 1]

As shown in Table 1, the cured products obtained by using the epoxy resin composition of the present invention (Examples 1 to 5), as compared with BPA (Comparative Example 2) which is an epoxy compound used for general use in the production of printed wiring boards, And showed extremely low dielectric loss tangent. Among them, an epoxy resin composition containing an epoxy compound modified with an aromatic carboxylic acid anhydride has realized a low absorption rate and a low dielectric constant while maintaining a high Tg, and it has been confirmed that the resin is suitable as a resin for forming a printed wiring board.

Claims (9)

(a) a mixture comprising an epoxy compound A represented by the formula [1] and a compound B which may have an epoxy group represented by the formula [2], and (b) a curing agent.
[Chemical Formula 1]

(Wherein R ¹ to R ³ each independently represent a hydrogen atom or a methyl group, and L ¹ to L ³ each independently represent an alkylene group having 1 to 10 carbon atoms.)
(2)

(Wherein, L ¹ to L ^3, and R ¹ represents the same meaning as defined above, X ¹ to X ³ each independently represents a group represented by the formula [2a] or formula [2b] (stage, X ¹ to And at least one of X ³ represents a group represented by the formula [2b]), R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 20 carbon atoms which may be substituted, or a carbon atom number An aryl group having 6 to 10 carbon atoms, and a black point representing a bond number. The method according to claim 1,
Wherein L ¹ to L ³ are an alkylene group selected from the group consisting of a methylene group, a trimethylene group, and a hexamethylene group. 3. The method according to claim 1 or 2,
Wherein R ⁴ and R ⁵ are an alkyl group of 1 to 10 carbon atoms which may be substituted. 4. The method according to any one of claims 1 to 3,
Wherein R ⁴ and R ⁵ are an alkyl group having 2 to 10 carbon atoms. 3. The method according to claim 1 or 2,
Wherein R &lt; ⁴ &gt; and R &lt; ⁵ &gt; are optionally substituted phenyl groups. 6. The method according to any one of claims 1 to 5,
An epoxy resin composition comprising 0.2 to 20 moles of the compound B per 1 mole of the epoxy compound A. 7. The method according to any one of claims 1 to 6,
Wherein the curing agent (b) is at least one selected from the group consisting of an acid anhydride, an amine, a phenol resin, a polyamide resin, an imidazole, and a polymercaptan. 8. The method according to any one of claims 1 to 7,
(B) a curing agent in an amount of 0.5 to 1.5 equivalents based on 1 equivalent of the epoxy group of the epoxy resin (a). A printed wiring board comprising a cured product of the epoxy resin composition according to any one of claims 1 to 8.