JP2010059242A - Epoxy resin curable composition, resin varnish, prepreg, metal-clad laminate, and cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin curable composition with both of low linear expansion and solder temperature resistance, and suitable for a print wiring board, etc., and to provide a resin varnish, a prepreg, a metal-clad laminate and a cured product using the composition. <P>SOLUTION: This epoxy resin curable composition includes a compound of a specific structure having a quinoxaline structure, and a phenolic hydroxyl group or an epoxy group. The resin varnish, the prepreg, the metal-clad laminate and the cured product using the composition are also disclosed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an epoxy resin curable composition containing a compound having a specific structure having a quinoxaline structure, a resin varnish, a prepreg, a metal-clad laminate and a cured product using the same.

  Epoxy resins are widely used for printed wiring boards used for electrical and electronic products because of their characteristics. In recent years, warpage of a printed wiring board has become a problem as the printed wiring board becomes thinner. As a measure for reducing the warpage, there is a low linear expansion of the epoxy resin. In recent years, lead-free solder has been promoted, and the use of lead-free solder having a relatively high soldering temperature is increasing. Therefore, in order to prevent quality deterioration due to heat during soldering, a printed wiring board having excellent solder heat resistance is required.

  As an epoxy resin, diglycidyl ether of bisphenol A is widely known as a general-purpose product, and as a curing agent, a polyphenol compound such as phenol novolak or dicyandiamide is widely known as a general-purpose product.

  Non-Patent Document 1 describes various epoxy resin curable compositions. Patent Documents 1 and 2 describe low linear expansion epoxy resin curable compositions containing various epoxy resins. However, in these conventional epoxy resin curable compositions, an inorganic filler that deteriorates physical properties such as workability and tensile strength is required, and thus sufficient performance in physical properties cannot be obtained.

  Patent Documents 3 and 4 describe highly heat-resistant epoxy resin curable compositions containing various epoxy resins. However, in these conventional epoxy resin curable compositions, sufficient performance in physical properties such as a coefficient of linear expansion could not be obtained.

JP 2004-335661 A JP 2004-359853 A JP 2001-233945 A JP 2001-278946 A “Review Epoxy Resin” Volume 1 p. 58, 61, 62, 148-150 Epoxy Resin Technology Association

  The present invention has excellent physical properties such as low linear expansion and high solder heat resistance, and is suitable for use as, for example, a printed wiring board, as well as a resin varnish, prepreg, and metal-clad using the same. It is an object to provide a laminate and a cured product.

  As a result of intensive studies to solve the above problems, the present inventors have used a phenol compound having a quinoxaline structure as a curing agent for an epoxy resin, or by using an epoxy resin having a quinoxaline structure. The present inventors have found that an epoxy resin curable composition having excellent physical properties such as heat resistance can be obtained and completed the present invention.

  That is, this invention provides the epoxy resin curable composition characterized by containing the compound represented by following General formula (1).

(Wherein, X ₁ and X ₂ are each independently an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, substituent a good carbon atoms of 1 to 12 alkoxy which may have Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of X ₁ and X ₂ Either or both have a phenolic hydroxyl group or an epoxy group, and X ₁ and X ₂ may be cross-linked with each other, in which case the structure in which X ₁ and X ₂ are cross-linked with each other is a saturated or unsaturated carbon. It is a ring structure having 3 to 8 atoms and has a phenolic hydroxyl group or an epoxy group, and Y ₁ and Y ₂ are each independently 1 carbon atom substituted with a substituent having a phenolic hydroxyl group or an epoxy group. -12 hydrocarbon group, C 1-12 a Kokishi group, an amino group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, .Y ₁ and Y ₂ represents a hydroxyl group or a hydrogen atom may be crosslinked each other, in which case, Y ₁ and The structure in which Y ₂ is cross-linked with each other is a saturated or unsaturated ring structure having 3 to 15 carbon atoms and has a phenolic hydroxyl group or an epoxy group, and Z ₁ and Z ₂ are each independently a substituent. An optionally substituted hydrocarbon group having 1 to 8 carbon atoms or an optionally substituted alkoxy group having 1 to 8 carbon atoms or a hydrogen atom, m represents an integer of 0 to 3; Is 2 or 3, the plurality of Z ₁ may be the same or different, and n represents an integer of 0 to 2.)

  Moreover, this invention provides the said epoxy resin curable composition containing the compound represented by following General formula (2).

Wherein R ₁ and R ₂ are each independently a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy having 1 to 12 carbon atoms which may have a substituent. Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of R ₁ and R ₂ Either or both have a phenolic hydroxyl group or an epoxy group, and Y ₁ and Y ₂ are each independently a hydrocarbon group having 1 to 12 carbon atoms substituted with a substituent having a phenolic hydroxyl group or an epoxy group. Represents an alkoxy group having 1 to 12 carbon atoms, an amino group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, a hydroxyl group, or a hydrogen atom, and Y ₁ and Y ₂ may be cross-linked to each other. good, in which case, Y ₁ and Y ₂ are crosslinked with one another structure A saturated or unsaturated ring structure of 3 to 15 carbon atoms, and .Z ₁ and Z ₂ having a phenolic hydroxyl group or epoxy group, each independently, optionally carbon atoms which may have a substituent 1 to 8 hydrocarbon group or an optionally substituted alkoxy group having 1 to 8 carbon atoms or a hydrogen atom, m represents an integer of 0 to 3, and when m is 2 to 3, Z ₁ may be the same or different, and n represents an integer of 0 to 2.)

  Moreover, this invention provides the said epoxy resin curable composition containing the compound represented by following General formula (3).

(Wherein, X ₁ and X ₂ are each independently an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, substituent a good carbon atoms of 1 to 12 alkoxy which may have group, an amino group which may 1 to 12 carbon atoms which may have a substituent, an amide group or a hydrogen atom may 1 to 12 carbon atoms which may have a substituent, any of X ₁ and X ₂ Either or both have a phenolic hydroxyl group or an epoxy group, n represents an integer of 0 to 2. Z ₁ and Z ₂ are each independently 1 to 1 carbon atoms which may have a substituent. 8 represents an alkoxy group having 1 to 8 carbon atoms or a hydrogen atom which may have a hydrocarbon group or a substituent, and _one of W ₁ and W ₂ represents a group having a glycidyloxy group or a phenolic hydroxyl group. represents and the other represents a group having a hydrogen atom, when n is 0, W ₁ and W ₂ One may represent a substituent having a phenolic hydroxyl group or epoxy group having a carbon number of 0-7.)

  Moreover, this invention provides the said epoxy resin curable composition containing the compound represented by following General formula (4).

(In the formula, B represents a hydrogen atom or a glycidyl group.)

  Moreover, this invention provides the said epoxy resin curable composition containing the compound represented by following General formula (5).

(In the formula, B represents a hydrogen atom or a glycidyl group.)

  Moreover, this invention provides the said epoxy resin curable composition containing the compound represented by following General formula (6).

(In the formula, B represents a hydrogen atom or a glycidyl group.)

  Moreover, this invention provides the said epoxy resin curable composition containing the compound represented by following General formula (7).

(In the formula, B represents a hydrogen atom or a glycidyl group.)

  Moreover, this invention provides the resin varnish containing the said epoxy resin curable composition and the organic solvent.

  Moreover, this invention provides the prepreg obtained by heating, after impregnating the said resin varnish in a glass woven fabric, a glass nonwoven fabric, or an organic fiber woven fabric.

  The present invention also provides a metal-clad laminate in which the prepreg and metal foil are laminated.

  Moreover, this invention provides the hardened | cured material formed by hardening | curing the said epoxy resin curable composition or the said resin varnish.

  According to the present invention, an epoxy resin curable composition having excellent physical properties such as a low coefficient of linear expansion and high solder heat resistance, and a resin varnish, prepreg, metal-clad laminate and cured product using the same are provided. Can do.

  Hereinafter, the present invention will be specifically described.

  The epoxy resin curable composition of this invention contains the compound represented by following General formula (1).

(Wherein, X ₁ and X ₂ are each independently an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, substituent a good carbon atoms of 1 to 12 alkoxy which may have Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of X ₁ and X ₂ Either or both have a phenolic hydroxyl group or an epoxy group, and X ₁ and X ₂ may be cross-linked with each other, in which case the structure in which X ₁ and X ₂ are cross-linked with each other is a saturated or unsaturated carbon. It is a ring structure having 3 to 8 atoms and has a phenolic hydroxyl group or an epoxy group, and Y ₁ and Y ₂ are each independently 1 carbon atom substituted with a substituent having a phenolic hydroxyl group or an epoxy group. -12 hydrocarbon group, C 1-12 a Kokishi group, an amino group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, .Y ₁ and Y ₂ represents a hydroxyl group or a hydrogen atom may be crosslinked each other, in which case, Y ₁ and The structure in which Y ₂ is cross-linked with each other is a saturated or unsaturated ring structure having 3 to 15 carbon atoms and has a phenolic hydroxyl group or an epoxy group, and Z ₁ and Z ₂ are each independently a substituent. An optionally substituted hydrocarbon group having 1 to 8 carbon atoms or an optionally substituted alkoxy group having 1 to 8 carbon atoms or a hydrogen atom, m represents an integer of 0 to 3; Is 2 or 3, the plurality of Z ₁ may be the same or different, and n represents an integer of 0 to 2.)

In the general formula (1), either one or both of X ₁ and X ₂ has a phenolic hydroxyl group, such as a hydroxyl group, an o-hydroxyphenyl group, an m-hydroxyphenyl group, or a p-hydroxyphenyl group. Is preferred.

In the general formula (1), examples of the group having an epoxy group which one or both of X ₁ and X ₂ have include an epoxy group, a glycidyl group, an alicyclic epoxy group, a glycidyloxy group, and these. An alkoxy group, an amino group, an amide group, and the like having a substituent as glycidyloxy group, o-glycidyloxyphenyl group, m-glycidyloxyphenyl group, or p-glycidyloxyphenyl group are preferable.

In said general formula (1), as a group which does not have an epoxy group and a phenolic hydroxyl group among X < ₁ > or X < ₂ >, for example, a C1-C12 hydrocarbon group which may have a substituent or C1-C12 alkoxy group which may have a substituent or C1-C12 amino group which may have a substituent or C1-C12 which may have a substituent In view of physical properties such as solder heat resistance and solubility, a phenyl group or a hydrogen atom is preferable.

In the general formula (1), the Y ₁ and Y _2, solder heat resistance, from the viewpoint of physical properties such as solubility, hydroxyl, glycidyl oxy group.

In the general formula (1), Z ₁ and Z ₂ are each a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent or an alkoxy having 1 to 8 carbon atoms which may have a substituent. Although it may be a group or a hydrogen atom, a phenyl group, a hydrogen atom, a methyl group, or an ethyl group is preferable from the viewpoint of physical properties such as solder heat resistance and solubility.

  In the general formula (1), m is an integer of 0 to 3, and m is preferably 0 from the viewpoints of solder heat resistance, solubility and the like.

  In said general formula (1), n is an integer of 0-2, and it is preferable that n is 0 from points, such as solder heat resistance and solubility.

Furthermore, Table Among the compounds represented by the general formula (1), from the viewpoint of production cost and physical properties, the compound having a quinoxaline structure, crosslinked Z ₁ and Z ₂ each other, the following general formula (2) The compound which is made is mentioned.

Wherein R ₁ and R ₂ are each independently a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy having 1 to 12 carbon atoms which may have a substituent. Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of R ₁ and R ₂ Either or both have a phenolic hydroxyl group or an epoxy group, and Y ₁ and Y ₂ are each independently a hydrocarbon group having 1 to 12 carbon atoms substituted with a substituent having a phenolic hydroxyl group or an epoxy group. Represents an alkoxy group having 1 to 12 carbon atoms, an amino group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, a hydroxyl group, or a hydrogen atom, and Y ₁ and Y ₂ may be cross-linked to each other. good, in which case, Y ₁ and Y ₂ are crosslinked with one another structure A saturated or unsaturated ring structure of 3 to 15 carbon atoms, and .Z ₁ and Z ₂ having a phenolic hydroxyl group or epoxy group, each independently, optionally carbon atoms which may have a substituent 1 to 8 hydrocarbon group or an optionally substituted alkoxy group having 1 to 8 carbon atoms or a hydrogen atom, m represents an integer of 0 to 3, and when m is 2 to 3, Z ₁ may be the same or different, and n represents an integer of 0 to 2.)

In the above general formula (2), either one or both of R ₁ and R ₂ has a phenolic hydroxyl group, such as a hydroxyl group, an o-hydroxyphenyl group, an m-hydroxyphenyl group, or a p-hydroxyphenyl group. Is preferred.

In the general formula (2), examples of the group having an epoxy group which one or both of R ₁ and R ₂ have include an epoxy group, a glycidyl group, an alicyclic epoxy group, a glycidyloxy group, and these. An alkoxy group, an amino group, an amide group, and the like having a substituent as glycidyloxy group, o-glycidyloxyphenyl group, m-glycidyloxyphenyl group, or p-glycidyloxyphenyl group are preferable.

In the general formula (2), examples of the group having no epoxy group and phenolic hydroxyl group in R ₁ or R ₂ include a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or C1-C12 alkoxy group which may have a substituent or C1-C12 amino group which may have a substituent or C1-C12 which may have a substituent In view of physical properties such as solder heat resistance and solubility, a phenyl group or a hydrogen atom is preferable.

  Furthermore, among the compounds having a quinoxaline skeleton represented by the general formula (1), preferable compounds from the viewpoint of physical properties such as solder heat resistance and solubility include compounds represented by the following general formula (3). It is done.

(Wherein, X ₁ and X ₂ are each independently an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, substituent a good carbon atoms of 1 to 12 alkoxy which may have Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of X ₁ and X ₂ Either or both have a phenolic hydroxyl group or an epoxy group, n represents an integer of 0 to 2. Z ₁ and Z ₂ are each independently 1 to 1 carbon atoms which may have a substituent. 8 represents an alkoxy group having 1 to 8 carbon atoms or a hydrogen atom which may have a hydrocarbon group or a substituent, and _one of W ₁ and W ₂ represents a group having a glycidyloxy group or a phenolic hydroxyl group. represents and the other represents a group having a hydrogen atom, when n is 0, W ₁ and W ₂ One may represent a substituent having a phenolic hydroxyl group or epoxy group having a carbon number of 0-7.)

In the general formula (3), either one or both of X ₁ and X ₂ has a phenolic hydroxyl group, such as a hydroxyl group, an o-hydroxyphenyl group, an m-hydroxyphenyl group, or a p-hydroxyphenyl group. It is preferable that

In the general formula (3), examples of the group having an epoxy group which one or both of X ₁ and X ₂ have include an epoxy group, a glycidyl group, an alicyclic epoxy group, a glycidyloxy group, and these. An alkoxy group, an amino group, an amide group, and the like having a substituent as glycidyloxy group, o-glycidyloxyphenyl group, m-glycidyloxyphenyl group, or p-glycidyloxyphenyl group are preferable.

In the general formula (3), the group having no epoxy group and a phenolic hydroxyl group of X ₁ or X _2, for example, good 1 to 12 carbon atoms which may have a substituent a hydrocarbon group or C1-C12 alkoxy group which may have a substituent or C1-C12 amino group which may have a substituent or C1-C12 which may have a substituent In view of physical properties such as solder heat resistance and solubility, a phenyl group or a hydrogen atom is preferable.

In the general formula (3), Z ₁ and Z ₂ are each a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent or an alkoxy having 1 to 8 carbon atoms which may have a substituent. Although it may be a group or a hydrogen atom, a phenyl group, a hydrogen atom, a methyl group, or an ethyl group is preferable from the viewpoint of physical properties such as solder heat resistance and solubility.

  In said general formula (3), n is an integer of 0-2, and it is preferable that n is 0 from the point of manufacturing cost.

In the general formula (3), either W ₁ or W ₂ represents a group having a glycidyloxy group or a phenolic hydroxyl group, the other represents a group having a hydrogen atom, and when n is 0, W ₁ And W ₂ may represent a substituent having a phenolic hydroxyl group or an epoxy group having 0 to 7 carbon atoms. From the viewpoint of physical properties such as solder heat resistance and solubility, either W ₁ or W ₂ is o-hydroxyphenyl group, m-hydroxyphenyl group, p-hydroxyphenyl group, glycidyloxy group or o-glycidyloxy. It is preferably a phenyl group, m-glycidyloxyphenyl group or p-glycidyloxyphenyl group, and the other is preferably a hydrogen atom or a methyl group.

  The compound having a quinoxaline structure represented by the general formulas (1) to (3) may be a mixture of a plurality of structural isomers. The case where such a mixture has a phenolic hydroxyl group will be described more specifically below.

  Examples of a mixture of a plurality of structural isomers when the compound represented by the general formula (1) has a phenolic hydroxyl group include the following mixtures 1 and 2. Moreover, the following mixture 3 is mentioned as an example of the mixture of a some structural isomer when the compound represented by General formula (2) has a phenolic hydroxyl group. Moreover, the following mixture 4 is mentioned as an example of the mixture of a some structural isomer when the compound represented by General formula (3) has a phenolic hydroxyl group. However, the present invention is not limited in any way by the following structure.

  As a method for synthesizing a mixture of a plurality of structural isomers when the compound represented by the general formula (1) has a phenolic hydroxyl group, by synthesizing a quinoxaline ring from a diaminobenzene derivative and a glyoxal derivative, The method of containing a quinoxaline structure is mentioned. The mixture 1 will be described in detail by taking the above example as an example, and quinoxaline ring synthesis is performed as shown in the following reaction formula A. That is, the mixture 1 can be obtained by reacting 3,4-diaminophenol and p-hydroxyphenylglyoxal in a solvent to quinoxalination reaction. It is preferable to use an acid catalyst such as acetic acid or trifluoroacetic acid because the reaction is accelerated.

  Next, the case where the mixture of a plurality of structural isomers of the compound having a quinoxaline structure represented by the general formulas (1) to (3) has an epoxy group will be described more specifically.

  Examples of the mixture of a plurality of structural isomers when the compound represented by the general formula (1) has an epoxy group include the following mixtures 5 and 6. Moreover, the following mixture 7 is mentioned as an example of the mixture of several structural isomers in case the compound represented by General formula (2) has an epoxy group. Moreover, the following mixture 8 is mentioned as an example of the mixture of a some structural isomer in case the compound represented by General formula (3) has an epoxy group. However, the present invention is not limited in any way by the following structure.

  When the compound represented by the general formula (1) has an epoxy group, the method for synthesizing a mixture of a plurality of structural isomers will be described in detail by taking the above mixture 5 as an example. And a method obtained by reacting the mixture 1 with epichlorohydrin in a solvent in the presence of a base.

  The epoxy resin curable composition of this invention may contain the compound represented by General formula (1)-(3) as a hardening | curing agent of an epoxy resin, and may contain it as an epoxy resin. As an aspect which uses this compound as a hardening | curing agent, for example, when the compounds represented by the general formulas (1) to (3) have a phenolic hydroxyl group, a mixture of a plurality of structural isomers, that is, the general formula (1 ) Have a phenolic hydroxyl group (for example, mixtures 1 and 2), when the compound represented by general formula (2) has a phenolic hydroxyl group (for example, mixture 3), The use of a mixture when the represented compound has a phenolic hydroxyl group (for example, mixture 4) can be exemplified. Moreover, as an aspect which uses the compound represented by General Formula (1)-(3) as an epoxy resin, for example, when this compound has an epoxy group, it is a mixture of a plurality of structural isomers, that is, the general formula ( When the compound represented by 1) has an epoxy group (for example, mixtures 5 and 6), when the compound represented by the general formula (2) has an epoxy group (for example, mixture 7), it is represented by the general formula (3). The use of a mixture when the compound to be produced has an epoxy group (for example, mixture 8) can be exemplified. In any of the above embodiments, the epoxy resin curable composition of the present invention may contain other curing agents known as curing agents and other epoxy resins known as epoxy resins, alone or in combination of two or more. it can.

  As said other hardening | curing agent, if normally used as a hardening | curing agent of a general epoxy resin, there will be no restriction | limiting in particular, Amines, phenols, an acid anhydride, etc. are mentioned. Examples of amines include xylylenediamine, 1-cyanoguanidine, diaminodiphenylmethane, diaminodiphenylsulfone, methylenedianiline, metaphenylenediamine, and the like. Examples of the phenols include biphenol, bisphenol A, bisphenol F, phenol novolak, cresol novolak, bisphenol A novolak, and alkyl group-substituted products thereof. Acid anhydrides include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, chlorendic anhydride, nadic acid anhydride, methyl nadic anhydride, dodecylnyl succinic anhydride, phthalic anhydride, methyl hexahydro anhydride Examples include phthalic acid and maleic anhydride. These can be used alone or in combination of two or more.

  The other epoxy resin is not particularly limited. For example, bisphenol A novolac type epoxy resin, bisphenol F novolac type epoxy resin, biphenyl type bifunctional epoxy resin, biphenyl modified novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthol-cresol co-condensed novolak type epoxy Resin, naphthol-phenol co-condensation novolak epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, triphenylmethane epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, tetraphenylethane epoxy resin, naphthol A novolak-type epoxy resin is mentioned. These can be used alone or in combination of two or more.

  The amount of the curing agent used in the epoxy resin curable composition of the present invention is not particularly limited, and the ratio between the number of reactive functional groups of the curing agent (α) and the number of epoxy groups of the epoxy resin (β) is It is preferable to blend so that α / β = 0.8 to 1.2 / 1.0. It is more preferable that α / β = 0.9 to 1.0 / 1.0.

  It is preferable that an epoxy equivalent is 100-1000 g / eq for a part or all of the epoxy resin in the epoxy resin curable composition of the present invention.

  The epoxy resin curable composition of the present invention may contain an inorganic filler. The inorganic filler is not particularly limited as long as it is usually used in a general epoxy resin curable composition. For example, aluminum hydroxide, magnesium hydroxide, E glass powder, alumina, magnesium oxide, dioxide dioxide Titanium, potassium titanate, calcium silicate, calcium carbonate, clay, talc and the like can be mentioned, and these can be used alone or in combination. The inorganic filler can also be surface treated with a silane coupling agent or the like.

  The amount of the inorganic filler used is the sum (γ) of the mass of all the epoxy resins used in the epoxy resin curable composition and the mass of all the curing agents used, and the mass of the inorganic filler (δ). The ratio is preferably γ / δ = 1.0 to 95.0 / 1.0.

  You may add the hardening accelerator which accelerates | stimulates reaction with an epoxy resin and a hardening | curing agent to the epoxy resin curable composition of this invention. Examples of the curing accelerator include imidazole compounds, amines, boron trifluorides, and organic phosphines. Examples of imidazole compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2. -Methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazo Trimium nitrate, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazo Rutorimeriteto, 1-cyanoethyl-2-phenyl-4,5-di (cyano ethoxymethyl) imidazole, and the like. Examples of amines include dimethylaminomethylphenol-2,4,6-tri (dimethylaminomethyl) phenol, tri-2-ethylhexane salt of tri (dimethylaminomethyl) phenol, and the like. Examples of boron trifluoride include boron trifluoride / monoethylamine complex, boron trifluoride / triethylamine complex, boron trifluoride / piperidine complex, boron trifluoride / n-butyl ether complex Compounds, boron trifluoride / amine complex compounds, and the like. Examples of organic phosphines include triphenylphosphine, diphenylphosphine, and tributylphosphine.

  The curing accelerator is preferably blended in an amount of 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of the epoxy resin and the curing agent. From the viewpoint of the storage stability of the prepreg, 0.1 part by mass or more is preferable, and from the viewpoint of shortening the processing time, 5 parts by mass or less is preferable. More preferably, it is 0.15 to 2 parts by mass.

  Furthermore, the epoxy resin curable composition of the present invention can also contain a silane coupling agent.

  The present invention also provides a resin varnish containing the above-described epoxy resin curable composition and an organic solvent. Typically, the epoxy resin curable composition is dissolved or dispersed in an organic solvent. Examples of the organic solvent include ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as toluene and xylene, 2-methoxyethanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, Ether solvents such as propylene glycol monobutyl ether, aprotic nitrogen-containing solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolidinone, N-methylpyrrolidone, and γ-butyrolactone Illustrated. These may be used alone or in combination of two or more. The content of the organic solvent in the resin varnish is preferably 25% by mass to 75% by mass in consideration of, for example, the impregnation property of the resin varnish into a woven fabric or a nonwoven fabric when a prepreg described below is produced.

  The present invention also provides a prepreg using the above-described resin varnish. The prepreg can be obtained by impregnating the resin varnish of the present invention described above into a base fabric made of a woven fabric or a nonwoven fabric, typically a glass woven fabric, a glass nonwoven fabric or an organic fiber woven fabric, and heating. More typically, for example, a glass woven fabric, a glass nonwoven fabric or an organic fiber woven fabric is impregnated with a resin varnish obtained by dissolving or dispersing the epoxy resin curable composition of the present invention in an organic solvent, and then heated. Can be formed by drying the solvent in the resin varnish and partially curing the epoxy resin curable composition. Hereinafter, the case where a glass cloth is used as the base fabric will be described more specifically.

  The glass cloth is impregnated with the resin varnish as follows: (A) The resin varnish is accumulated in a bath, passed through the glass cloth while being immersed, and then slits or mangles so that the glass cloth is impregnated with a predetermined amount. And (i) a method of impregnating by applying a predetermined amount of resin varnish directly on a glass cloth with a roll coater, a die coater, a gravure coater or the like.

  Moreover, after impregnating the said resin varnish to a glass cloth, the method of heating and drying a solvent and partially hardening resin can use well-known methods, such as a hot air and electromagnetic waves. The temperature at the time of heat drying is preferably 110 ° C. or higher, and preferably 200 ° C. or lower in order to suppress evaporation, volatilization, thermal decomposition and thermal degradation of the epoxy resin curable composition. Further, the heat drying time is preferably 20 seconds or more and less than 20 minutes, more preferably 30 seconds or more and less than 15 minutes. Moreover, in order to adjust the fluidity of the prepreg produced in a series of steps, it is possible to heat the prepreg with a batch type oven or the like, or to continuously heat it again with a continuous heating device. It is also possible to perform pretreatment such as a method of impregnating the glass cloth with an organic solvent in advance before impregnating the glass cloth with the resin varnish.

  The mass content of the glass cloth in the prepreg in the prepreg state (hereinafter referred to as “glass content”) is preferably 80% by mass or less, more preferably 75% by mass or less. The lower limit of the glass content can be a value that does not impair the dimensional stability of the metal-clad laminate obtained in the present invention, but is usually 20% by mass or more. When the glass content of the prepreg exceeds 80% by mass, a prepreg in which the resin is present only in the yarn bundle portion of the glass fiber fabric tends to be difficult to form a laminated sheet.

The glass cloth used for the prepreg of the present invention may be any glass cloth such as E glass, C glass, D glass, and S glass. In the glass cloth, the weave density is preferably 10 to 200/25 mm, more preferably 15 to 100/25 mm, and the mass is preferably 5 to 400 g / m ² , more preferably 8 to 300 g / m ^2. Plain weave, satin weave, twill weave, Nanako weave, etc. can be used. Moreover, the glass cloth woven by the glass yarn in which both or one of the warp and the weft was textured may be used. Also, a glass cloth at a stage where a sizing agent necessary for weaving is attached, a glass cloth at a stage where the sizing agent is removed, or a glass cloth at a stage where a silane coupling agent or the like is already treated by a known surface treatment method Either of these may be used. Further, it may be a glass cloth that has been subjected to physical processing such as fiber opening or flattening with a columnar flow or a water flow by a high frequency vibration method.

  The present invention also provides a metal-clad laminate in which the above prepreg and metal foil are laminated. The metal-clad laminate can be used, for example, as a printed wiring board material for electric and electronic products. Typically, a metal-clad laminate in which a prepreg and a metal foil are laminated is obtained by sandwiching one or a plurality of prepregs sandwiched between metal foils and heating and pressing to form a single piece. Although metal foil is not specifically limited, For example, copper foil etc. can be used according to a use.

  This invention also provides the hardened | cured material which hardened the epoxy resin curable composition mentioned above or the resin varnish mentioned above. The epoxy resin curable composition of the present invention can be applied to various applications by being cured, for example, in the state of being present in the above-described prepreg. Curing conditions can be appropriately selected according to the composition of the epoxy resin curable composition or the resin varnish. For example, the temperature is raised from room temperature to 150 to 230 ° C. at an average of 1 to 20 ° C./min, and after being held for 0.5 to 10 hours in the range of 150 to 230 ° C., it is cooled to room temperature at an average of 1 to 100 ° C./min A press pressure may be applied as necessary from the temperature rise to the cooling, or the pressure may be reduced.

  Next, the present invention will be described with reference to examples and comparative examples.

  The examples illustrate the invention in detail. Examples 1-4 are examples of a mixture of a plurality of structural isomers of a compound having an epoxy group or a phenolic hydroxyl group. According to the formulation shown in Table 1, a resin varnish was prepared using a mixture of a plurality of structural isomers of a compound having an epoxy group. Moreover, in Comparative Examples 1-3, the resin varnish was prepared using the comparison epoxy resin by the mixing | blending of Table 1. The mass part in Table 1 is the solid content ratio excluding the solvent.

  Using the obtained resin varnish, a test piece was prepared by the following preparation method, and the solder heat resistance and the linear expansion coefficient were tested by the following test method. The results are shown in Table 1.

  [Example 1 (Synthesis example of mixture 1 and mixture 5)]

(Synthesis example of mixture 1)
In a 200 mL three-necked flask under a nitrogen stream, Organic & Biomolecular Chemistry 2003 Volume 1 p. The reaction mixture was charged with 1.24 g (10 mmol) of 3,4-diaminophenol synthesized by the method described in 4347, 1.50 g (10 mmol) of p-hydroxyphenylglyoxal, 50 mL of acetic acid, and 5 mL of toluene while refluxing for 10 hours. The condensate obtained by azeotropically cooling and evaporating vapor was separated by oil / water, and the reaction was carried out by returning the oil from which water was removed to the reaction system. After completion of the reaction, toluene was removed under reduced pressure, 10 mL of 1 mol / L hydrochloric acid was added, 100 mL of water was added, and the precipitate was collected by filtration. After washing with distilled water, mixture 1 was obtained by removing acetic acid and water under reduced pressure.

(Synthesis example of mixture 5)
Under a nitrogen stream, 1.26 g (5 mmol) of Mixture 1, 9.25 g (100 mmol) of epichlorohydrin, and 30 mL of N, N-dimethylsulfoxide were charged into a 200 mL three-necked flask, and the system temperature was raised to 60 ° C. After uniformly dissolving, 40.0 parts by mass of sodium hydroxide aqueous solution 1.00 g (sodium hydroxide 10 mmol) was added dropwise over 1 hour. During this time, the temperature was gradually raised, and the temperature inside the system was 80 ° C. at the end of the dropping. Thereafter, the reaction was allowed to proceed at 80 ° C. for 30 minutes. After cooling the system temperature to room temperature, 100 mL of distilled water was added, and the precipitate was collected by filtration. After washing with distilled water to remove by-product salts, epichlorohydrin, water, and N, N dimethyl sulfoxide were removed under reduced pressure to obtain a mixture 5. The epoxy equivalent of the obtained mixture 5 was 185 g / eq.

  [Example 2 (Synthesis example of mixture 2 and mixture 6)]

(Synthesis example of mixture 2)
Under a nitrogen stream, 10.0 g (50 mmol) of 1,2,4-triaminobenzene dihydrochloride and 40 mL of N-methyl-2-pyrrolidone were charged into a 1 L 3-neck flask and dissolved uniformly. While maintaining the reaction system at room temperature, 40.0 parts by mass of sodium hydroxide aqueous solution 10.0 g (sodium hydroxide 100 mmol) was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 1 hour. 7.50 g (50 mmol) of p-hydroxyphenylglyoxal, 250 mL of acetic acid, and 25 mL of toluene were added to the system, and the reaction mixture was refluxed for 10 hours. The reaction was carried out by separating the water and returning the oil from which water was removed to the reaction system. After completion of the reaction, toluene was removed under reduced pressure, 500 mL of water was added, and the precipitate was collected by filtration. Washed with distilled water. After recrystallization using ethanol, the precipitate was collected by filtration, and ethanol was removed under reduced pressure to obtain 6-amino-2-p-hydroxyphenylquinoxaline and 7-amino-2-p-hydroxyphenylquinoxaline. A mixture of was obtained.

  Under a nitrogen stream, 10.0 g (40 mmol) of a mixture of 6-amino-p-hydroxyphenylquinoxaline and 7-amino-p-hydroxyphenylquinoxaline obtained as described above in a 500 mL three-necked flask, N, N-dimethyl 100 mL of acetamide was charged and dissolved uniformly. A solution prepared by dissolving 5.52 g (40 mmol) of p-hydroxybenzoic acid chloride in 50 mL of N, N-dimethylacetamide was dropped over 15 minutes while maintaining the temperature in the reaction system at 0 ° C. with an ice bath. After completion of the dropwise addition, the temperature in the reaction system was raised to 60 ° C. and stirred for 5 hours while maintaining 60 ° C. After cooling the reaction system to room temperature, 300 mL of distilled water was added, and the precipitate was collected by filtration. After washing with distilled water to remove by-product salts, water 2 and N, N-dimethylacetamide were removed under reduced pressure to obtain a mixture 2.

(Synthesis example of mixture 6)
Mixture 6 was obtained from Mixture 2 in a manner similar to the method of preparing Mixture 5 from Mixture 1 described in Example 1. The epoxy equivalent of the obtained mixture 6 was 246 g / eq.

  [Example 3 (Synthesis example of mixture 3 and mixture 7)]

(Synthesis example of mixture 3)
Under a nitrogen stream, 5.68 g (20 mmol) of tetrahydrochloric acid 1,2,4,5-tetraaminobenzene and 10 mL of N-methyl-2-pyrrolidone were charged into a 500 L three-necked flask and dissolved uniformly. While maintaining the reaction system at room temperature, 40.0 parts by mass of sodium hydroxide aqueous solution 8.00 g (sodium hydroxide 80 mmol) was added dropwise over 15 minutes, and the mixture was stirred at room temperature for 1 hour. To the system, 6.00 g (40 mmol) of p-hydroxyphenylglyoxal, 100 mL of acetic acid, and 10 mL of toluene were added to the system and refluxed for 10 hours. The reaction was carried out by separating the water and returning the oil from which water was removed to the reaction system. After completion of the reaction, toluene was removed under reduced pressure, 20 mL of 1 mol / L hydrochloric acid was added, 300 mL of water was added, and the precipitate was collected by filtration. After washing with distilled water to remove by-product salts, acetic acid and water were removed under reduced pressure to obtain a mixture 3.

(Synthesis example of mixture 7)
Mixture 7 was obtained from Mixture 3 in a manner similar to the method of preparing Mixture 5 from Mixture 1 described in Example 1. The epoxy equivalent of the obtained mixture 7 was 249 g / eq.

  [Example 4 (Synthesis example of mixture 4 and mixture 8)]

(Synthesis example of mixture 4)
Mixture 4 was prepared by preparing Mixture 3 as described in Example 3, except that tetrahydrochloric acid 3,3 ′, 4,4′-biphenyltetraamine was used instead of tetrahydrochloric acid 1,2,4,5-tetraaminobenzene. Obtained in a similar manner.

(Synthesis example of mixture 8)
Mixture 8 was obtained from mixture 4 in a manner similar to the method of preparing mixture 5 from mixture 1 described in Example 1. The epoxy equivalent of the obtained mixture 8 was 295 g / eq.

[Comparative Examples 1-3]
Below, the comparative epoxy resin used by the comparative example is shown.

  The epoxy equivalent of the comparative epoxy resin 1 was 136 g / eq.

  The epoxy equivalent of the comparative epoxy resin 2 was 169 g / eq.

  As comparative epoxy resin 3, JER604 manufactured by Japan Epoxy Resin Co., Ltd. was used. The epoxy equivalent of the epoxy resin 3 was 180 g / eq.

  As the curing agent 1, MEH-7851-4H manufactured by Meiwa Kasei Co., Ltd. was used. The OH equivalent of the curing agent 1 was 241 g / eq.

[Test method]
(1) Linear expansion coefficient A resin varnish was applied to a thickness of 160 μm on a metal plate whose surface was roughened, and partially cured by drying in an oven at 130 ° C. for 10 minutes. Subsequently, it was heated in an oven at 190 ° C. for 3 hours. After cooling to room temperature, it was processed into a size of 3 mm × 18.5 mm with a cutter knife to prepare a test piece for measuring the linear expansion coefficient. Using this test piece, a heating expansion curve was measured with TMA-50 manufactured by Shimadzu Corporation. The linear expansion coefficient was calculated from the elongation in the range of 40 ° C to 100 ° C.

(2) Solder heat resistance test A resin varnish was applied and impregnated on a glass woven fabric having a thickness of 100 μm, and heated at a temperature of 130 ° C. to prepare a prepreg. Four obtained prepregs were superposed, a copper foil having a thickness of 12 μm was superposed on the upper and lower surfaces thereof, and a copper clad laminate was produced by heating and pressing at 200 ° C. and 20 kg / cm ² for 3 hours. The copper foil on the surface of the copper clad laminate was removed by etching treatment, washed with water, and then processed into a size of 40 mm × 40 mm with a cutter knife to prepare a test piece for a solder heat resistance test. The test piece was dried in an oven at 120 ° C. and left in a saturated pressure cooker at 121 ° C. for 3 hours, and then quickly cooled in cold water so that the test piece did not dry. After wiping off the moisture on the surface of the test piece, the test piece was immersed in a solder bath adjusted to 288 ° C. for 30 seconds, and visually inspected for abnormalities such as swelling on the surface. In Table 1, ◯ represents that there was no abnormality such as swelling, and X represents that there was abnormality such as swelling.

  As is clear from the above Examples and Comparative Examples, the present invention provides a printed wiring board having both low linear expansion and solder heat resistance by using a compound having a quinoxaline skeleton represented by the general formula (1). An epoxy resin curable composition suitable for the above can be obtained.

  The epoxy resin curable composition, resin varnish, prepreg, metal-clad laminate and cured product of the present invention are useful in the field of printed wiring boards used for electric and electronic products, for example.

Claims (11)

The following general formula (1):

(Wherein, X ₁ and X ₂ are each independently an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, substituent a good carbon atoms of 1 to 12 alkoxy which may have Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of X ₁ and X ₂ Either or both have a phenolic hydroxyl group or an epoxy group, and X ₁ and X ₂ may be cross-linked with each other, in which case the structure in which X ₁ and X ₂ are cross-linked with each other is a saturated or unsaturated carbon. It is a ring structure having 3 to 8 atoms and has a phenolic hydroxyl group or an epoxy group, and Y ₁ and Y ₂ are each independently 1 carbon atom substituted with a substituent having a phenolic hydroxyl group or an epoxy group. -12 hydrocarbon group, C 1-12 a Kokishi group, an amino group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, .Y ₁ and Y ₂ represents a hydroxyl group or a hydrogen atom may be crosslinked each other, in which case, Y ₁ and The structure in which Y ₂ is cross-linked with each other is a saturated or unsaturated ring structure having 3 to 15 carbon atoms and has a phenolic hydroxyl group or an epoxy group, and Z ₁ and Z ₂ are each independently a substituent. An optionally substituted hydrocarbon group having 1 to 8 carbon atoms or an optionally substituted alkoxy group having 1 to 8 carbon atoms or a hydrogen atom, m represents an integer of 0 to 3; Is 2 or 3, the plurality of Z ₁ may be the same or different, and n represents an integer of 0 to 2.)
The epoxy resin curable composition characterized by containing the compound represented by these. The following general formula (2):

Wherein R ₁ and R ₂ are each independently a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, or an alkoxy having 1 to 12 carbon atoms which may have a substituent. Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of R ₁ and R ₂ Either or both have a phenolic hydroxyl group or an epoxy group, and Y ₁ and Y ₂ are each independently a hydrocarbon group having 1 to 12 carbon atoms substituted with a substituent having a phenolic hydroxyl group or an epoxy group. Represents an alkoxy group having 1 to 12 carbon atoms, an amino group having 1 to 12 carbon atoms, an amide group having 1 to 12 carbon atoms, a hydroxyl group, or a hydrogen atom, and Y ₁ and Y ₂ may be cross-linked to each other. good, in which case, Y ₁ and Y ₂ are crosslinked with one another structure A saturated or unsaturated ring structure of 3 to 15 carbon atoms, and .Z ₁ and Z ₂ having a phenolic hydroxyl group or epoxy group, each independently, optionally carbon atoms which may have a substituent 1 to 8 hydrocarbon group or an optionally substituted alkoxy group having 1 to 8 carbon atoms or a hydrogen atom, m represents an integer of 0 to 3, and when m is 2 to 3, Z ₁ may be the same or different, and n represents an integer of 0 to 2.)
The epoxy resin curable composition of Claim 1 containing the compound represented by these. The following general formula (3):

(Wherein, X ₁ and X ₂ are each independently an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, substituent a good carbon atoms of 1 to 12 alkoxy which may have Represents a group, an amino group having 1 to 12 carbon atoms which may have a substituent, an amide group having 1 to 12 carbon atoms which may have a substituent, or a hydrogen atom, and any _one of X ₁ and X ₂ Either or both have a phenolic hydroxyl group or an epoxy group, n represents an integer of 0 to 2. Z ₁ and Z ₂ are each independently 1 to 1 carbon atoms which may have a substituent. 8 represents an alkoxy group having 1 to 8 carbon atoms or a hydrogen atom which may have a hydrocarbon group or a substituent, and _one of W ₁ and W ₂ represents a group having a glycidyloxy group or a phenolic hydroxyl group. represents and the other represents a group having a hydrogen atom, when n is 0, W ₁ and W ₂ One may represent a substituent having a phenolic hydroxyl group or epoxy group having a carbon number of 0-7.)
The epoxy resin curable composition of Claim 1 or 2 containing the compound represented by these. The following general formula (4):

(In the formula, B represents a hydrogen atom or a glycidyl group.)
The epoxy resin curable composition of Claim 1 or 2 containing the compound represented by these. The following general formula (5):

(In the formula, B represents a hydrogen atom or a glycidyl group.)
The epoxy resin curable composition of Claim 1 containing the compound represented by these. The following general formula (6):

(In the formula, B represents a hydrogen atom or a glycidyl group.)
The epoxy resin curable composition of Claim 1 or 2 containing the compound represented by these. The following general formula (7):

(In the formula, B represents a hydrogen atom or a glycidyl group.)
The epoxy resin curable composition of Claim 1 or 3 containing the compound represented by these.   A resin varnish containing the epoxy resin curable composition according to claim 1 and an organic solvent.   A prepreg obtained by heating after impregnating the resin varnish according to claim 8 into a glass woven fabric, a glass nonwoven fabric or an organic fiber woven fabric.   A metal-clad laminate obtained by laminating the prepreg according to claim 9 and a metal foil.   Hardened | cured material formed by hardening | curing the epoxy resin curable composition in any one of Claims 1-7, or the resin varnish of Claim 8.