JP2013253146A - Curable composition, cured product, and printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition in which an obtained cured product is excellent in heat resistance, low thermal expansion, moisture resistance, and flame retardancy; a cured product curing the same; and a printed wiring board.SOLUTION: A curable composition includes: an epoxy compound (A) containing a naphthalene skeleton; and a naphtholic compound (B) shown by structural formula 1. In the formula, each Rindependently denotes a hydrogen atom, an alkyl group, and an alkoxy group, and n denotes a repeating unit and denotes an integer of 2-10.

Description

  The present invention relates to a curable composition in which the obtained cured product is excellent in all of heat resistance, low thermal expansion, moisture solder resistance and flame retardancy, and a cured product obtained by curing the composition and a printed wiring board.

  Compositions composed of epoxy group-containing compounds and phenolic compounds are widely used as insulating materials for semiconductor encapsulants and printed wiring boards because their cured products are excellent in heat resistance, moisture resistance, solder resistance, insulation, etc. Yes.

  Among these, for printed wiring board applications, with the trend toward miniaturization and high performance of electronic equipment, it is required to realize high-density wiring by narrowing the wiring pitch, and as a semiconductor mounting method corresponding to this, Instead of the conventional wire bonding method, a flip chip connection method in which a semiconductor device and a wiring board are joined by solder balls has become the mainstream. In this flip-chip connection method, solder balls are placed between the wiring board and the semiconductor, and the whole is heated to reflow and join the solder. Therefore, the insulating material for the wiring board has higher heat resistance than ever before. In addition, low thermal expansion and moisture and solder resistance are required. In addition, halogen-based flame retardants such as bromine have been conventionally used for insulating materials for printed wiring boards in order to impart flame retardancy. However, there has been more movement to eliminate halogen-based flame retardants from the viewpoint of environmental harmony. There is a growing demand for the development of halogen-free and highly flame retardant materials.

  As a material particularly excellent in heat resistance, for example, a technique is known in which calixarene obtained by reacting resorcinol and paraaldehyde is used as a curing agent for an epoxy group-containing compound (see Patent Document 1). According to this method, although the heat resistance is improved as compared with the conventional technique using a phenol novolac resin, it does not meet the increasing demand level recently, and the low thermal expansion property, the moisture resistance, the solder resistance, and the flame resistance are not satisfied. The sex was not enough.

JP 2010-248368 A

  Therefore, the problem to be solved by the present invention is that the obtained cured product is excellent in all of heat resistance, low thermal expansion property, moisture solder resistance and flame retardancy, and cured product obtained by curing this. And providing a printed wiring board.

  As a result of intensive studies to solve the above problems, the present inventors have used a naphthalene skeleton-containing epoxy compound as a main agent, and a calixarene type obtained by reacting a naphthol compound and formaldehyde as a curing agent under predetermined conditions. It has been found that by using a naphthol compound, a cured product having excellent heat resistance, low thermal expansion, moisture solder resistance and flame resistance can be obtained, and the present invention has been completed.

That is, the present invention provides a naphthalene skeleton-containing epoxy compound (A),
Structural formula 1

(In the formula, each R ₁ independently represents a hydrogen atom, an alkyl group, or an alkoxy group, and n is a repeating unit and is an integer of 2 to 10.)
It contains the naphthol compound (B) represented by these, It is related with the curable composition characterized by the above-mentioned.

  The present invention further relates to a cured product obtained by curing the curable composition.

  The present invention further relates to a printed wiring board obtained by impregnating a reinforcing base material with a varnish composition obtained by further blending an organic solvent with the curable composition, and stacking a copper foil and heat-pressing it.

  According to the present invention, there are provided a curable composition in which the obtained cured product is excellent in all of heat resistance, low thermal expansion, moisture resistance, solder resistance and flame retardancy, and a cured product obtained by curing the cured product and a printed wiring board. can do.

1 is a GPC chart of the naphthol compound (B-1) obtained in Example 1. FIG. FIG. 2 is an MS spectrum of the naphthol compound (B-1) obtained in Example 1.

  Hereinafter, the present invention will be described in detail.

  The naphthalene skeleton-containing epoxy resin (A) used in the present invention may be any resin having a naphthalene skeleton in its resin structure. For example, diglycidyloxynaphthalene, naphthalene dimer type epoxy resin, naphthylene ether type epoxy resin, Examples include alkoxynaphthalene skeleton-containing epoxy resins, naphthol aralkyl type epoxy resins, cresol-naphthol / formaldehyde condensed novolac type epoxy resins.

Here, specific examples of diglycidyloxynaphthalene include 1,4-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene, and the like.

Next, the naphthalene dimer type epoxy resin specifically has the following structural formula (i):

(Wherein R 1 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a t-butyl group) bis (2,7-diglycidyloxy-1-naphthyl) methane represented by

  Structural formula (ii)

(In the formula, each R1 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a t-butyl group.)
Binaphthyl type epoxy resin represented by:

  Structural formula (iii)

(In the formula, each R1 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a t-butyl group.)
The carbonyl group containing naphthalene type epoxy resin represented by these is mentioned.

  Next, the naphthylene ether type epoxy resin has the following structural formula (iv)

(Wherein R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aralkyl group, m and n are each an integer of 0 to 2, and m or n Either one is 1 or more.)
An epoxy compound represented by formula (II), specifically, a structure represented by the following A-1 to A-10.

In the structural formulas A-1 to A-10, G represents a glycidyl group.

  Next, the epoxy resin containing an alkoxynaphthalene skeleton is an epoxy resin obtained by glycidyl etherifying a phenol resin obtained by reacting a phenol compound (a1), an alkoxynaphthalene (a2) and an aldehyde compound (a3). It is done.

  Here, the phenol compound (a1) used as a raw material has the following structural formula (2)

(Wherein R1 and R2 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 6 carbon atoms), specifically, phenol, resorcinol, Unsubstituted phenols such as hydroquinone, monosubstituted phenols such as cresol, ethylphenol, n-propylphenol, iso-propylphenol, t-butylphenol, xylenol, methylpropylphenol, methylbutylphenol, dipropylphenol, dibutylphenol Examples include substituted phenols.

  Among these, cresol and phenol are particularly preferable from the viewpoint of the dielectric properties of the cured product.

  Further, the alkoxynaphthalene (a2) has the following structural formula (3)

(Wherein R represents an alkyl group having 1 to 4 carbon atoms, R3, R4, and R5 each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group). 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1-ethoxynaphthalene, 1,4-dimethoxynaphthalene, -T-butoxynaphthalene etc. are mentioned.

  Among these, 2-methoxynaphthalene and 2,7-dimethoxynaphthalene are particularly preferable from the viewpoint of easily forming an alkoxynaphthalene skeleton at the molecular terminal, and 2-methoxynaphthalene is particularly preferable from the viewpoint of dielectric characteristics.

  Next, specific examples of the aldehyde compound (a3) include formaldehyde and glyoxal. Among these, formaldehyde is preferable because the cured product obtained has excellent flame retardancy and dielectric properties.

  Next, the naphthol aralkyl type epoxy resin specifically has the following structural formulas (v-1) to (v-5).

The epoxy resin represented by these is mentioned. Here, l in the structural formulas (v-1) to (v-5) is a repeating unit and is an integer of 0 to 9.

Next, the cresol-naphthol / formaldehyde condensed novolac type epoxy resin is specifically represented by the following structural formulas (w-1) (w-2)

  The epoxy resin represented by these is mentioned. Here, o in the structural formulas (w-1) and (w-2) is a repeating unit and is an integer of 0 to 9.

  Among the naphthalene skeleton-containing epoxy resins (A) described in detail above, particularly in the present invention, diglycidyloxynaphthalene and naphthalene dimer type epoxy resins are excellent in heat resistance in cured products and have little change in heat resistance after heat history. This is preferable from the standpoint that the effect of the present invention appears remarkably. Furthermore, among the naphthalene dimer type epoxy resins, the bis (2,7-diglycidyloxy-1-naphthyl) alkane represented by the structural formula (i) or the carbonyl represented by the structural formula (iii). A group-containing naphthalene-based epoxy resin is preferable from the viewpoint that such an effect becomes remarkable.

  Next, the naphthol resin (B) used in the present invention specifically has the following structural formula 1

(In the formula, each R ₁ independently represents a hydrogen atom, an alkyl group, or an alkoxy group, and n is a repeating unit and is an integer of 2 to 10.)
It has the resin structure represented by these.

  Thus, the naphthol compound (B) used in the present invention has a so-called calixarene-type cyclic structure, and as a result, molecular motion in the cured product of the naphthol compound (B) is suppressed, resulting in excellent heat resistance. And low thermal expansibility. Further, such a rigid ring structure is advantageous for formation of char during combustion when used in combination with the naphthalene skeleton-containing epoxy resin (A), and exhibits high flame retardancy. In particular, when an epoxy compound having a relatively high functional group concentration is used, the crosslink density is increased to improve heat resistance, while flame retardancy is a problem. The present invention overcomes this.

  In the above structural formula 1, it is easy for the naphthol compound (B) to be produced when the site where the bonding position of the methylene group on the naphthalene ring has two bonding sites on the same ring. It is preferable from the point, and it is particularly preferable that a methylene group is bonded at the 2,4-position of the naphthalene ring from the point that a regular molecular structure is formed and the cured product is excellent in heat resistance and low thermal expansion. .

  In addition, n in the structural formula 1 is an integer of 2 to 10, and is preferably 2, 4, 6, or 8 from the viewpoint that the chemical structure is excellent and the effect of improving the heat resistance is remarkably exhibited. In particular, 4 is most preferable.

  Such naphthol compound (B) can be identified by confirming the molecular weight of the theoretical structure in the MS spectrum.

R ₁ in the structural formula 1, as described above, a hydrogen atom, an alkyl group, or an alkoxy group. Here, examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a tertiary butyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropyloxy group. And an alkoxy group having 1 to 4 carbon atoms such as a tertiary butyloxy group. In the present invention, it is more preferable that R1 is a hydrogen atom, a methyl group, an ethyl group, or a methoxy group, and among these, a hydrogen atom is particularly preferable because a cured product having excellent heat resistance can be obtained.

  In addition, the naphthol skeleton in the structural formula 1 may be either an α-naphthol skeleton or a β-naphthol skeleton, but is excellent in heat resistance in a cured product of the finally obtained epoxy compound and also has low thermal expansion. Since it is excellent, an α-naphthol skeleton is preferable. Furthermore, in the present invention, as the naphthol skeleton, an α-naphthol skeleton and a β-naphthol skeleton may coexist, and in this case, a cured product having more excellent heat resistance is obtained. The ratio of the β-naphthol compound to 1.2 mol or less per 1 mol of the α-naphthol compound is preferable.

  The above-mentioned naphthol compound (B) is, for example, a basic composition of naphthol compound and formaldehyde at a molar ratio (naphthol / formaldehyde) of 1.0 / 1.0 to 1.0 / 2.0. It can manufacture by the method of making it react in presence of a catalyst.

  Here, the said reaction can be specifically performed on 20-100 degreeC temperature conditions.

  Specific examples of the naphthol compound used in the reaction include α-naphthol, 1-hydroxy-3-methylnaphthalene, 1-hydroxy-5-methylnaphthalene, 1-hydroxy-6-methylnaphthalene, and 1-hydroxy-5. -Ethylnaphthalene, 1-hydroxy-6-ethylnaphthalene, 1-hydroxy-5-propylnaphthalene, 1-hydroxy-6-propylnaphthalene, 1-hydroxy-5-butylnaphthalene, 1-hydroxy-6-butylnaphthalene, 1 -Hydroxy-5-methoxynaphthalene, 1-hydroxy-6-methoxynaphthalene, 1-hydroxy-5-ethoxynaphthalene, 1-hydroxy-6-ethoxynaphthalene, 1-hydroxy-5-propyloxynaphthalene, 1-hydroxy-6 -Propyloxynaphthalene, 1 Α-naphthol compounds such as hydroxy-5-butyloxynaphthalene and 1-hydroxy-6-butyloxynaphthalene; β-naphthol, 2-hydroxy-3-methylnaphthalene, 2-hydroxy-5-methylnaphthalene, 2-hydroxy- 6-methylnaphthalene, 2-hydroxy-5-ethylnaphthalene, 2-hydroxy-6-ethylnaphthalene, 2-hydroxy-5-propylnaphthalene, 2-hydroxy-6-propylnaphthalene, 2-hydroxy-5-butylnaphthalene, 2-hydroxy-6-butylnaphthalene, 2-hydroxy-5-methoxynaphthalene, 2-hydroxy-6-methoxynaphthalene, 2-hydroxy-5-ethoxynaphthalene, 2-hydroxy-6-ethoxynaphthalene, 2-hydroxy-5 -Propyloxyna Examples include β-naphthol compounds such as thalene, 2-hydroxy-6-propyloxynaphthalene, 2-hydroxy-5-butyloxynaphthalene, and 2-hydroxy-6-butyloxynaphthalene. Since it is excellent in the heat resistance in the hardened | cured material of a compound, it is preferable that it is an alpha-naphthol compound, and it is especially preferable that it is alpha-naphthol.

  In the present invention, the α-naphthol compound and the β-naphthol compound may be used in combination. In that case, the β-naphthol compound is 1.2 mol or less with respect to 1 mol of the α-naphthol compound. It is preferable to use from the viewpoint of heat resistance.

  On the other hand, examples of the formaldehyde source used in the reaction include formalin, paraformaldehyde, trioxane and the like. Here, it is preferable that formalin is 30-60 mass% formalin from the point of water dilutability and workability | operativity at the time of manufacture.

  Specific examples of the basic catalyst used in the reaction include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred from the viewpoint of excellent catalytic activity. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.

  The amount of the basic catalyst used at this time is preferably 0.02 mol or more with respect to 1 mol of the naphthol compound because the calixarene structure can be easily formed. Furthermore, the molar ratio (naphthol compound / formaldehyde) is preferably 1.0 or less because the selectivity of the naphthol-type calix (4) arene compound, which is the most preferred molecular structure, can be enhanced. Here, the naphthol-type calix (4) arene compound is a compound in which four molecules of a naphthol compound are bonded via a methylene bond to form a cyclic structure.

  The blending ratio of the naphthalene skeleton-containing epoxy compound (A) and the naphthol compound (B) in the curable composition of the present invention is not particularly limited, but the obtained cured product is superior in heat resistance. Therefore, the ratio in which the total of phenolic hydroxyl groups contained in the naphthol compound (B) is in the range of 0.7 to 1.5 equivalents relative to 1 equivalent in total of the epoxy groups of the epoxy compound (A). It is preferable that

  In addition to the naphthalene skeleton-containing epoxy compound (A) and the naphthol compound (B), the curable composition of the present invention further comprises using a naphthol compound (B ′) other than the naphthol compound (B). This is preferable because the solvent solubility of the product is improved and the adjustment of the composition for a printed wiring board is facilitated.

  Specifically, the naphthol compound (A ′) used here is 2,7-dihydroxynaphthalene, α-naphthol novolak resin, β-naphthol novolak resin, α-naphthol / β-naphthol co-condensation type novolak resin, naphthol aralkyl. Examples thereof include naphthol resins such as resins and 1,1-bis (2,7-hydroxy-1-naphthyl) alkane.

  Among these, particularly from the point of excellent compatibility with the naphthol compound (A), 2,7-dicyanatonaphthalene, α-naphthol novolak cyanate ester resin, β-naphthol novolak cyanate ester resin, or α-naphthol / β-naphthol co-condensation type novolak is preferred.

  In particular, in the present invention, when the naphthol compound (B) is produced, β-naphthol is used in combination with α-naphthol, and a mixture of the calixarene naphthol compound and α-naphthol / β-naphthol co-condensation type novolak is obtained. A product obtained by producing a mixture of the naphthol compound (B) and α-naphthol / β-naphthol co-condensation type novolak by the method to obtain is preferable from the viewpoint of excellent solvent solubility.

  The content ratio of the naphthol compound (B) and the naphthol compound (B ′) is 3 to 50% based on the area ratio of the naphthol compound (B ′) when the mixture of both is measured by GPC. The ratio is preferably from the viewpoint of heat resistance and solvent solubility.

Here, the GPC measurement conditions specifically include the following conditions.
(GPC measurement conditions)
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  In the curable composition of the present invention, in addition to the naphthol compound (B) and the naphthol compound (B ′), other curing agents (B ″) are used as long as the solubility of the resin component in the organic solvent is not impaired. The amount of other curing agent (B ″) used is preferably in the range of 5 to 50% by mass in the total curing agent component, for example.

  Examples of the other curing agent (B ″) include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like. Specific examples of amine compounds include diaminodiphenylmethane. , Diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives and the like.

  Examples of the amide compound include polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.

  Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, And methyl hexahydrophthalic anhydride.

  Examples of the phenolic compounds include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition type resins, phenol aralkyl resins (Zylok resins), and resorcin novolac resins. Polyhydric phenol novolak resin, trimethylol methane resin, tetraphenylol ethane resin, biphenyl modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified Phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring-modified novolak resins (forma Phenol nucleus and an alkoxy group polyhydric phenol compound-containing aromatic ring are connected) polyhydric phenol compounds such as are mentioned in dehydrogenase. Among these other curing agent components, the phenolic compound is preferable because of its excellent curability.

  In the case where the curable composition of the present invention contains the naphthol compound (B ′) or other curing agent (B ′) in addition to the naphthalene skeleton-containing epoxy compound (A) and the naphthol compound (B), these The total proportion of phenolic hydroxyl groups contained in all curing agent components is in the range of 0.7 to 1.5 equivalents relative to a total of 1 equivalent of epoxy groups contained in the naphthalene skeleton-containing epoxy compound (A). This ratio is preferable from the viewpoint of good curability and excellent heat resistance of the cured product.

  In the present invention, an epoxy compound (A ′) other than the naphthalene skeleton-containing epoxy compound (A) may be used in combination. It is preferable that the usage-amount of another epoxy resin (A ') is the range used as 5-50 mass% in all the epoxy components, for example.

  As the epoxy compound (A ′) that can be used here, various epoxy resins can be used. For example, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins, Biphenyl type epoxy resins such as tetramethylbiphenyl type epoxy resins; phenol novolac type epoxy resins, cresol novolak type epoxy resins, bisphenol A novolac type epoxy resins, and epoxy compounds of condensates of phenolic compounds and aromatic aldehydes having phenolic hydroxyl groups , Novolac type epoxy resins such as biphenyl novolac type epoxy resins; triphenylmethane type epoxy resins; tetraphenylethane type epoxy resins; dicyclopentadiene-phenol addition reaction type Epoxy resins; phenol aralkyl type epoxy resins; phosphorus-containing epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Here, as the phosphorus atom-containing epoxy resin, epoxidized product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones Epoxidized phenolic resin obtained by reacting phenolic resin, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol noboc type epoxy resin with HCA, bisphenol A type epoxy resin and HCA Examples thereof include an epoxy resin obtained by modification with a phenol resin obtained by reacting with quinones.

  When the curable composition of this invention contains the said epoxy resin (A ') in addition to the said epoxy compound (A) and the said polyphenylene ether resin (B), these compounding ratios are in a curable composition. Curability is good that the total of phenolic hydroxyl groups contained in all curing agent components is in a range of 0.7 to 1.5 equivalents relative to a total of 1 equivalent of epoxy groups contained in all epoxy components. It is preferable from the viewpoint of excellent heat resistance of the cured product.

  In this invention, a hardening accelerator can also be used together suitably as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor sealing material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that 2-ethyl-4-methylimidazole is used for imidazole compounds, and triphenylphosphine is used for phosphorus compounds. For fins and tertiary amines, 1,8-diazabicyclo- [5.4.0] -undecene (DBU) is preferred.

  When adjusting the curable composition of this invention explained in full detail above to the varnish for printed wiring boards, etc., it is preferable to mix | blend an organic solvent (C) other than said each component. Examples of the organic solvent that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The amount used can be appropriately selected depending on the application. For example, in printed wiring board applications, it is preferable to use a polar solvent having a boiling point of 160 ° C. or less, such as methyl ethyl ketone, acetone, dimethylformamide, and the non-volatile content of 40 to 80% by mass. It is preferable to use in the ratio which becomes. On the other hand, in build-up adhesive film applications, examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, and cellosolve. It is preferable to use carbitol solvents such as butyl carbitol, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, and the non-volatile content is 30 to 60% by mass. It is preferable to use in proportions.

  In order to further improve the flame retardancy, the curable composition of the present invention may contain a non-halogen flame retardant that substantially does not contain a halogen atom, for example, in printed wiring board applications.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of thermosetting resins such as phenolic resin, and (iii) thermosetting of phenolic resin on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide or titanium hydroxide. For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of phosphorus-based flame retardant, other components of the curable composition, and the desired degree of flame retardancy. For example, epoxy components, curing agents, non- and In 100 parts by mass of the curable composition in which all other fillers and additives are blended, when red phosphorus is used as a non-halogen flame retardant, it may be blended in the range of 0.1 to 2.0 parts by mass. Preferably, when an organic phosphorus compound is used, it is preferably blended in the range of 0.1 to 10.0 parts by mass, and particularly preferably in the range of 0.5 to 6.0 parts by mass.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Ii) co-condensates of phenolic compounds such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine and formaldehyde; ) A mixture of the cocondensate of (ii) and a phenol resin such as a phenol formaldehyde condensate, (iv) Those obtained by further modifying (ii) and (iii) with paulownia oil, isomerized linseed oil, etc. It is done.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass, especially in 0.1 to 10 parts by mass, in 100 parts by mass of the curable composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 5 parts by mass.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy component, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

  Specific examples of the low-melting-point glass include, for example, Shipley (Bokusui Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3-based, ZnO-P2O5-MgO-based, P2O5-B2O3-PbO-MgO-based, Examples thereof include glassy compounds such as P—Sn—O—F, PbO—V 2 O 5 —TeO 2, Al 2 O 3 —H 2 O, and lead borosilicate.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.5 to 50 parts by mass, particularly 5 to 30 parts by mass, in 100 parts by mass of the curable composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to blend in the range of parts.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organic metal salt-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.005 to 10 parts by mass in 100 parts by mass of the curable composition containing all of the epoxy component, curing agent, non-halogen flame retardant and other fillers and additives.

  An inorganic filler can be mix | blended with the curable composition of this invention as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably in the range of 0.5 to 100 parts by mass in 100 parts by mass of the curable composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the curable composition of this invention as needed.

  The curable composition of this invention is obtained by mixing each above-mentioned component uniformly. The curable composition of the present invention in which an epoxy component, a curing agent and, if necessary, a curing accelerator are blended can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications for which the curable composition of the present invention is used include printed wiring board materials, resin casting materials, adhesives, interlayer insulation materials for build-up substrates, and adhesive films for build-up. Among these various applications, in printed circuit boards, insulating materials for electronic circuit boards, and adhesive films for build-up, passive parts such as capacitors and active parts such as IC chips are embedded in so-called electronic parts. It can be used as an insulating material for a substrate. Among these, it is preferable to use for the printed wiring board material and the adhesive film for buildup from the characteristics, such as high heat resistance and a flame retardance.

  Here, in order to produce a printed circuit board from the curable composition of the present invention, a resin composition blended with the organic solvent (C) and varnished is impregnated into a reinforcing base material, and a copper foil is overlaid and heated. The method of making it crimp is mentioned. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, the varnish-like curable composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., so that a prepreg as a cured product is obtained. obtain. Although it does not specifically limit as a mass ratio of the curable composition used at this time and a reinforcement base material, Usually, it is preferable to prepare so that the resin part in a prepreg may be 20-60 mass%. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours, A desired printed circuit board can be obtained.

  When the curable composition of the present invention is used as a resist ink, for example, a cationic polymerization catalyst is used as a catalyst for the curable composition, and a pigment, talc, and filler are further added to form a resist ink composition. Then, after apply | coating on a printed circuit board by a screen printing system, the method of setting it as a resist ink hardened | cured material is mentioned.

  When the curable composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the curable composition to obtain a composition for an anisotropic conductive film, which is liquid at room temperature Examples of the method include a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  As a method for obtaining an interlayer insulating material for a build-up substrate from the curable composition of the present invention, for example, the curable composition appropriately blended with rubber, filler and the like is applied to a wiring substrate on which a circuit is formed by a spray coating method, a curtain After applying using a coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. Moreover, a roughened surface is formed by heat-pressing a copper foil with resin obtained by semi-curing the curable composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to produce a build-up substrate by omitting this process.

  The method for producing an adhesive film for buildup from the curable composition of the present invention is, for example, applied for a multilayer printed wiring board by applying the curable composition of the present invention on a support film to form a resin composition layer. The method of setting it as an adhesive film is mentioned.

  When the curable composition of the present invention is used for an adhesive film for build-up, the adhesive film is softened under a lamination temperature condition (usually 70 ° C. to 140 ° C.) in a vacuum laminating method. It is important to show fluidity (resin flow) capable of filling the via hole or through hole in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the above-mentioned adhesive film is prepared by preparing the varnish-like curable composition of the present invention, and then applying the varnish-like composition to the surface of the support film (y). It can be produced by drying the organic solvent by heating or blowing hot air to form the layer (x) of the curable resin composition.

  The thickness of the formed layer (x) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the layer (x) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the curable composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The support film (y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, a method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (x) is protected with a protective film, after peeling these layers ( x) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

  The lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 × 10 4 to 107.9 × 104 N / m 2), and the air pressure is 20 mmHg (26 It is preferable to laminate under a reduced pressure of 0.7 hPa or less.

  What is necessary is just to heat the composition obtained by the said method in the temperature range about 20-250 degreeC as a method of obtaining the hardened | cured material of this invention.

Next, the present invention will be described in more detail with reference to examples and comparative examples.
"" Is based on mass unless otherwise specified. The softening point, 13C-NMR, GPC and MS were measured under the following conditions.

1) Softening point measurement method: JIS K7234

2) 13C-NMR: Measurement conditions are as follows.
Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination)
Solvent: Dimethyl sulfoxide pulse angle: 45 ° C pulse Sample concentration: 30 wt%
Integration count: 10,000 times

3) GPC: The measurement conditions are as follows.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

4) MS: Double Density Mass Spectrometer AX505H (FD505 manufactured by JEOL Ltd.)
H)

Production Example 1 Production of Naphthol Compound (B-1) 216 parts by mass of α-naphthol (1.50 mol), 37% by mass formaldehyde was added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer. 146 parts by mass (1.80 mol) of an aqueous solution, 121 parts by mass of isopropyl alcohol, and 46 parts by mass (0.56 mol) of a 49% aqueous sodium hydroxide solution were added and stirred at room temperature while blowing nitrogen. Then, it heated up at 80 degreeC and stirred for 1 hour. After completion of the reaction, 40 parts by mass of first sodium phosphate was added for neutralization, and then cooled and the crystalline substance was filtered off. Then, after repeating washing | cleaning 3 times with 200 mass parts of water, it dried under heating and pressure reduction, and obtained 224 mass parts of naphthol compounds (B-1). The hydroxyl group equivalent of the obtained naphthol compound (B-1) was 156 g / equivalent. A GPC chart of the obtained naphthol compound is shown in FIG. 1, and an MS spectrum is shown in FIG. From the MS spectrum, 624 peaks corresponding to the compound in the case of n = 4 in the structural formula 1 were detected. Moreover, the content rate of the compound corresponding to the case of n = 4 in the said Structural formula 1 calculated from a GPC chart was 85.6%.

Production Example 2 Production of Naphthol Resin Mixture (B-2) 216 parts by mass (1.50 mol) of α-naphthol was converted into 144 parts by mass of α-naphthol (1.00 mol) and 72 parts by mass of β-naphthol (0.50 mol). ) Was used in the same manner as in Production Example 1 to obtain 199 parts by mass of naphthol resin mixture (B-2). The resulting naphthol resin mixture (B-2) had a hydroxyl equivalent of 158 grams / equivalent. From the MS spectrum, 624 peaks showing n = 4 in Structural Formula 1 were detected. Moreover, the content rate of n = 4 body in the said Structural formula 1 computed from a GPC chart was 32.8%. Therefore, the naphthol resin mixture (B-2) was found to be a mixture of a naphthol compound of n = 4 in the structural formula 1 and an α-naphthol / β-naphthol cocondensation type novolak.

Production Example 3 Production of Epoxy Resin Mixture (A-1) 240 parts (1.50 mol) of 2,7-dihydroxynaphthalene was added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer. A 37 mass% formaldehyde aqueous solution 85 parts (1.05 mol), isopropyl alcohol 376 parts, and a 48% potassium hydroxide aqueous solution 88 parts (0.75 mol) were charged and stirred at room temperature while blowing nitrogen. Then, it heated up at 75 degreeC and stirred for 2 hours. After completion of the reaction, 108 parts of first sodium phosphate was added for neutralization, isopropyl alcohol was removed under reduced pressure, and 480 parts of methyl isobutyl ketone was added. The obtained organic layer was repeatedly washed with 200 parts of water three times, and then methyl isobutyl ketone was removed by heating under reduced pressure to obtain 245 parts of a phenol compound (a-1).

Subsequently, 84 parts (hydroxyl group 1.0 equivalent) of the phenol compound (a-1) obtained by the above reaction while performing a nitrogen gas purge on a flask equipped with a thermometer, a condenser, and a stirrer, 463 parts of epichlorohydrin (5.0 parts) Mol) and 53 parts of n-butanol were charged and dissolved. After the temperature was raised to 50 ° C., 220 parts (1.10 mol) of a 20% aqueous sodium hydroxide solution was added over 3 hours, and then further reacted at 50 ° C. for 1 hour. After completion of the reaction, unreacted epichlorohydrin was distilled off under reduced pressure at 150 ° C. 300 parts of methyl isobutyl ketone and 50 parts of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 15 parts of a 10% by mass sodium hydroxide aqueous solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 parts of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 126 parts of an epoxy resin mixture (A-1). The resulting epoxy resin mixture (A-1) had a softening point of 95 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) of 9.0 dPa · s, and an epoxy equivalent of 170. Gram / equivalent. Further, the mixture (A-1), the structural formulas epoxy compound 39.6 wt% of all R ¹ a hydrogen atom (i), the in the structural formula (iii) all of R ¹ is a hydrogen atom It contained 10.5% by mass of the epoxy compound and 49.9% by mass of other oligomer components.

Comparative Production Example 1 Production of resorcin-type calixarene (b-1) 33.0 parts by mass (0.3 mol) of resorcinol was added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer. It melt | dissolved in 120 mass parts, 40 mass parts of concentrated hydrochloric acid was added under ice-cooling, and it stirred for 30 minutes at about 5 degreeC. To this was added dropwise 12.1 parts by mass (0.1 mol) of paraaldehyde, followed by heating to reflux for about 30 minutes. The reaction mixture was cooled to room temperature and a solid produced by filtration was obtained. The obtained solid was washed once with water and three times with methanol, recrystallized twice with methanol, and then vacuum-dried at 60 ° C. for 24 hours to obtain 22 parts by mass of resorcin-type calixarene (b-1). It was. The obtained resorcin-type calixarene (b-1) was a white solid and had a hydroxyl group equivalent of 68 grams / equivalent.

Examples 1 and 2 and Comparative Example 1
In accordance with the formulation shown in Table 1 below, “HP-4032” (diglycidyloxynaphthalene, epoxy equivalent of 152 g / equivalent) manufactured by DIC as an epoxy compound, “HP-4700” manufactured by DIC [R in the above structural formula (i) ¹ is all hydrogen, epoxy equivalent 165 grams / equivalent], or the epoxy resin mixture (A-1) as a curing agent (B-1), (B-2), or (b-1). Then, 2-ethyl-4-methylimidazole (2E4MZ) was blended as a curing accelerator, and methyl ethyl ketone was blended and adjusted so that the nonvolatile content (NV) of each composition was finally 58% by mass. . Subsequently, it was cured under the following conditions to make a test piece, and the heat resistance, thermal expansion coefficient, and moisture resistance and solder resistance were evaluated by the following methods. The results are shown in Table 1.

Test piece preparation conditions The compound prepared above was molded by a press at a temperature of 150 ° C. for 10 minutes, and then cured at a temperature of 175 ° C. for 5 hours.

Heat resistance test The glass transition temperature of the test piece was measured by the DMA method. Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric, rectangular tension method; frequency 1 Hz, heating rate 3 ° C./min), the elastic modulus change is maximized (tan δ change rate is the highest). The (large) temperature was evaluated as the glass transition temperature. Temperature rising speed 3 ℃ / min

Linear expansion coefficient A test piece was cut into a size of 5 mm × 5 mm × 0.8 mm, and thermomechanical analysis was performed in a compression mode using a thermomechanical analyzer (TMA: SS-6100 manufactured by Seiko Instruments Inc.).

Measurement conditions Measurement weight: 88.8mN
Temperature increase rate: 2 times at 3 ° C / minute Measurement temperature range: -50 ° C to 300 ° C
The measurement under the above conditions was performed twice for the same sample, and the average expansion coefficient in the temperature range from 240 ° C. to 280 ° C. in the second measurement was evaluated as the linear expansion coefficient.

Moisture resistance and solder resistance A test piece (25 mm × 50 mm) was immersed in boiling distilled water at 100 ° C. for 2 hours, and then immersed in a solder bath at 260 ° C. for 30 seconds, and the state change before and after that was observed.
○: No change in appearance △: No more than 5 blisters with a diameter of 5 mm or less.
×: Swelling larger than 5 mm in diameter, or 6 or more swells having a diameter of 5 mm or less

A test piece for evaluation having a width of 12.7 mm, a length of 127 mm, and a thickness of 1.6 mm was prepared under the above conditions by using a composition in which 50% by mass of an inorganic filler with respect to the resin solid content was filled, and UL- In accordance with the 94 test method, a combustion test was performed using five test pieces.

Claims (9)

A naphthalene skeleton-containing epoxy compound (A),
Structural formula 1

(In the formula, each R ₁ independently represents a hydrogen atom, an alkyl group, or an alkoxy group, and n is a repeating unit and is an integer of 2 to 10.)
The curable composition characterized by containing the naphthol compound (B) represented by these. The curable composition according to claim 1, further comprising a naphthol compound (B ') other than the naphthol compound (B) in addition to the naphthalene skeleton-containing epoxy compound (A) and the naphthol compound (B). The curable composition according to claim 2, wherein the naphthol compound (B ') is a naphthol novolac resin. The naphthol compound (B) and the naphthol compound (B ′) are contained in such a ratio that the area ratio of the naphthol compound (B ′) to the total area of the GPC chart of the mixture of both is in the range of 3 to 50%. The curable composition according to claim 2. The curable composition according to claim 1, wherein the naphthalene skeleton-containing epoxy compound (A) is a diglycidyl ether of dihydroxynaphthalene. The naphthalene skeleton-containing epoxy compound (A) has the following structural formula (i)

2. The curable resin composition according to claim 1, which is a tetrafunctional epoxy compound represented by the formula: wherein R1 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a t-butyl group. object.
The naphthalene skeleton-containing epoxy compound (A) is represented by the following structural formula (iii)

2. The curable resin according to claim 1, which is a naphthalene skeleton-containing epoxy compound represented by the formula (wherein R1 independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a t-butyl group). Composition. Hardened | cured material formed by hardening | curing the curable composition as described in any one of Claims 1-7. A printed wiring obtained by impregnating a reinforcing base material with a varnish composition further blended with the curable composition according to any one of claims 1 to 7 and then hot-pressing the copper foil. substrate.

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