JP5326188B2 - Resin composition, phenoxy resin, coating composition, adhesive composition, adhesive film, prepreg, multilayer printed wiring board, and resin-coated copper foil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in low dielectric constant, low dielectric loss tangent, compatibility and heat resistance, to provide a phenoxy resin used for the resin composition, and to provide a coating material composition, adhesive agent composition, adhesive film, prepreg, resin-clad copper foil and multilayer printed wiring board using the resin composition. <P>SOLUTION: There are provided the resin composition containing a phenoxy resin (A) having a naphthalene skeleton and a structure wherein the hydrogen atoms of hydroxyl groups are substituted by acyl groups and having a weight average mol.wt. of 5,000-200,000, and a solvent (B); the coating material composition, adhesive agent composition, adhesive film, prepreg, resin-clad copper foil and multilayer printed wiring board containing the resin composition; and the phenoxy resin having the structure represented by general formula (1) and a weight average mol.wt. of 5,000-200,000. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention is a coating composition, adhesive composition, adhesive film, ink composition excellent in heat resistance, especially interlayer insulation materials such as multilayer printed wiring boards having low dielectric constant, dielectric loss tangent and excellent heat resistance, mechanical properties, It can be preferably used for build-up materials, electrical insulating materials such as semiconductor insulating materials, adhesive films, prepregs, resin-coated copper foils and the like. Furthermore, the present invention relates to a resin composition having a low dielectric constant and dielectric loss tangent, excellent heat resistance and mechanical properties, excellent compatibility with various resins and good solvent solubility, and a phenoxy resin contained in the resin composition. .

  Epoxy resins are widely used in paint, civil engineering, architecture, and electrical applications. For example, high molecular weight bisphenol A type epoxy resin, also called phenoxy resin, is added to base resin for paint and film molding, epoxy resin varnish to adjust fluidity, and toughness when cured. Those used for improving additives and the like, and those having a bromine atom in the skeleton are blended with thermoplastic resins and used as flame retardants.

  On the other hand, in the electrical applications, printed wiring boards used for electrical and electronic equipment are becoming increasingly dense due to the increase in the number of layers in the build-up method, in which conductor layers and organic insulating layers are alternately stacked. Yes. For this reason, there is an increasing demand for electrical insulation characteristics such as low water absorption, low dielectric constant, and low dielectric loss tangent, as well as adhesion and heat resistance of the organic insulating layer used in the printed wiring board. As a resin composition excellent in low dielectric constant and low dielectric loss tangent, for example, 5 mol% to 99% of the hydroxyl group of polyhydroxy ether having a bisphenol skeleton and / or a phenyl skeleton contained in the skeleton is an ester. A resin composition containing a thermoplastic resin and a thermosetting resin as essential components is disclosed. (For example, refer to Patent Document 1). However, the resin composition has insufficient compatibility with other resins and heat resistance.

International Publication No. 2005/095517 Pamphlet

  An object of the present invention is to provide a resin composition excellent in low dielectric constant, low dielectric loss tangent, compatibility with other resins, and heat resistance, a phenoxy resin used in the resin composition, and further using the resin composition. The object is to provide a coating composition, an adhesive composition, an adhesive film, a prepreg, a resin-coated copper foil, and a multilayer printed wiring board.

As a result of intensive studies, the present inventors have found the following findings (1) to (7).
(1) By using a thermoplastic resin containing a naphthalene skeleton in place of the thermoplastic resin disclosed in Patent Document 1, a low dielectric constant, low without limiting the amount of esterification in the thermoplastic resin A resin composition having excellent dielectric loss tangent, compatibility with other resins, and heat resistance.
(2) The composition containing the resin composition is excellent in compatibility with the resin, solvent solubility, and heat resistance, and can be suitably used as a coating composition.
(3) The composition containing the resin composition is excellent in compatibility with the resin, solvent solubility, and heat resistance, and can be suitably used as an adhesive composition.
(4) An adhesive film formed by forming a thin film of the resin composition on a support base film has a low dielectric constant, a low dielectric loss tangent and excellent heat resistance.
(5) A prepreg obtained by coating and / or impregnating the resin composition on a sheet-like reinforcing base material has a low dielectric constant, a low dielectric loss tangent and excellent heat resistance.
(6) A multilayer printed wiring board in which a plated conductor layer is formed on the cured product of the resin composition and the other surface is closely adhered to the patterned circuit board is heat-resistant with a low dielectric constant and a low dielectric loss tangent To be excellent.
(7) The resin-coated copper foil formed by applying the resin composition has a low dielectric constant and a low dielectric loss tangent and is excellent in heat resistance.
The present invention has been completed based on the above findings.

  That is, the present invention contains a phenoxy resin (A) having a structure in which a naphthalene skeleton and a hydrogen atom of a hydroxyl group are substituted with an acyl group and having a weight average molecular weight of 5,000 to 200,000, and a solvent (B). A resin composition characterized by the above is provided.

  In addition, the present invention provides a phenoxy resin having a structure represented by the following general formula (1) and having a weight average molecular weight of 5,000 to 200,000.

（式中、Ａは、水素原子または下記一般式（２）で表される基である。また、Ｒ_１炭素原子数１〜２０の炭化水素基を有するアシル基で、ａは２０以上である。）

(In the formula, A is a hydrogen atom or a group represented by the following general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a is 20 or more. .)

  Furthermore, this invention provides the coating composition characterized by containing the said resin composition resin composition.

  Furthermore, this invention provides the adhesive composition characterized by containing the said resin composition resin composition.

  Furthermore, this invention provides the adhesive film characterized by forming the thin film of the said resin composition resin composition on a support base film.

  Furthermore, the present invention provides a prepreg characterized by coating and / or impregnating a sheet-like reinforcing substrate made of fibers with the resin composition.

  Furthermore, the present invention is characterized in that a plated conductor layer is formed on a cured product obtained by curing the resin composition resin composition, and the other surface is laminated in close contact with the patterned internal circuit board. A multilayer printed wiring board is provided.

  Furthermore, this invention provides the copper foil with a resin characterized by apply | coating the said resin composition to copper foil.

  According to the present invention, it is possible to provide a resin composition excellent in low dielectric constant, low dielectric loss tangent, compatibility with other resins, and heat resistance. Moreover, the phenoxy resin used for the said resin composition can also be provided. By using the resin composition of the present invention, it is possible to provide a coating composition and an adhesive composition that are excellent in compatibility with a resin, solvent solubility, and heat resistance, and have a low dielectric constant, low dielectric loss tangent, and heat resistance. Adhesive films, prepregs, multilayer printed wiring boards and resin-coated copper foils that are excellent in properties can also be provided.

  The phenoxy resin (A) used in the present invention has a naphthalene skeleton and a structure in which part or all of the hydrogen atoms in the hydroxyl group are substituted with acyl groups, and has a weight average molecular weight (MW) of 5,000 to 200. 1,000 phenoxy resin. Here, if the weight average molecular weight is less than 5,000, the film-forming property and the mechanical properties are deteriorated, which is not preferable. If the weight average molecular weight is larger than 200,000, the compatibility is undesirably lowered. The weight average molecular weight is more preferably 10,000 to 100,000.

  As described above, the phenoxy resin (A) used in the present invention has a structure in which a hydrogen atom in a hydroxyl group of the phenoxy resin (A) is substituted with an acyl group. By having such a structure, it is difficult to crystallize and has a low polarity, and since it has good compatibility with the resin and solvent solubility, it is easy to handle, and an effect of being excellent in low dielectric constant, low dielectric loss tangent, and heat resistance can be obtained. As a phenoxy resin (A) used by this invention, the esterified phenoxy resin of this invention mentioned later is mentioned, for example.

The content of the naphthalene skeleton of the phenoxy resin (A) is preferably 10 to 60% by weight based on the weight of the phenoxy resin (A) because a phenoxy resin having excellent heat resistance, compatibility, and solubility can be obtained. 15 to 55% by weight is more preferable. Here, the content of naphthalene skeleton referred to in the present invention is obtained by dividing the molecular weight of the naphthalene skeleton portion by the total weight of the phenoxy resin. For example, in the case of the phenoxy resin (A1) as shown in Synthesis Example 6, the weight of each naphthalene skeleton (—C ₁₀ H ₆ —) in the naphthalene type epoxy resin and dihydroxy naphthalene resin is (100 × 126) / 272 = 46. 3, (55.6 × 126) /160=43.8, and the content of the naphthalene skeleton in the total phenoxy resin is obtained by dividing the weight of the naphthalene skeleton portion by the weight of the entire phenoxy resin. (46.3 + 43.8) / (100 + 55.6 + 39.4 × 42/102) × 100 = 52.4 (%).

  Here, “100” is the weight of the naphthalene type epoxy resin used in Synthesis Example 1 described later, “126” is the molecular weight of the naphthalene skeleton, and “272” is the molecular weight of the naphthalene type epoxy resin. Said “55.6” is the weight of dihydroxynaphthalene used in Synthesis Example 1, and “160” is the molecular weight of dihydroxynaphthalene. The total weight of the phenoxy resin is, for example, in Synthesis Example 6 in which a hydrogen atom in the hydroxyl group is substituted with an acetyl group, and the weight of the substituted acetyl group must be incorporated into the total weight of the phenoxy resin. In Synthesis Example 6, 39.4 g of acetic anhydride (molecular weight 102) is used to introduce an acetyl group into the phenoxy resin. The molecular weight of the acetyl group bonded to the phenoxy resin by substitution with a hydrogen atom in the hydroxyl group of the phenoxy resin is 42, and the weight of the acetyl group bonded to the phenoxy resin is the amount used × (the molecular weight of the acetyl group bonded to the phenoxy resin / Molecular weight of acetic anhydride), that is, (39.4 × 42) / 102.

  As a phenoxy resin (A) used by this invention, as a ratio by which the hydrogen atom in the hydroxyl group which phenoxy resin (A) has was substituted by the acyl group, 1 mol%-100 mol% are low, and a dielectric constant and a dielectric loss tangent are low. It is preferable because it becomes a phenoxy resin excellent in compatibility, solubility, and non-crystallinity, more preferably 10 to 100 mol%, more preferably 50 to 100 mol%, and other phenoxy resin ( From the viewpoint of good esterification efficiency in preparing A), 70 to 95 mol% is more preferable.

  Examples of the structure in which the hydrogen atom in the hydroxyl group of the phenoxy resin (A) used in the present invention is substituted with an acyl group include, for example, a structure having no active hydrogen obtained by esterifying a hydroxyl group with a monovalent acid, and a large number of hydroxyl groups. Examples include a structure having a carboxylic acid esterified with a basic acid or the like, a structure having a hydroxyl group esterified with a lactone or the like. Among these, those having a structure without active hydrogen (a structure having no polar group) obtained by esterifying the hydroxyl group with a monovalent acid have dielectric properties, compatibility with resins, solubility, non-crystallinity, This is preferable because of ease of manufacture.

  As an acyl group substituted with the hydrogen atom of the hydroxyl group which phenoxy resin (A) has, the acyl group which has a C1-C20 hydrocarbon group is preferable. Therefore, as an acyl group substituted with the hydrogen atom of the hydroxyl group which phenoxy resin (A) has, the acyl group which has a C1-C20 hydrocarbon group and does not have active hydrogen is more preferable.

  Examples of the hydrocarbon group having 1 to 20 carbon atoms that the acyl group has include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, and vinyl. Group, benzyl group, naphthyl group, phenethyl group and the like. Among them, an acyl group having a hydrocarbon group having 1 to 6 carbon atoms is more preferable, a methyl group or a benzyl group is more preferable, and a methyl group is further preferable.

  As described later, the phenoxy resin (A) used in the present invention is composed of a bifunctional epoxy resin and a bifunctional phenol compound in such a combination that at least one of the bifunctional epoxy resin and the bifunctional phenol compound contains a naphthalene skeleton. What was obtained by making it react is preferable. As the bifunctional epoxy resin used here, an epoxy resin containing a 3,3 ′, 5,5′-tetramethylbiphenol skeleton is preferred, and a phenol compound containing a naphthalene skeleton is more preferred as the bifunctional phenol compound.

  The phenoxy resin (A) used in the present invention is preferably a phenoxy resin containing a bisphenol S skeleton.

The phenoxy resin (A) used in the present invention can be obtained, for example, by esterifying a phenoxy resin in which a hydroxyl group is not esterified (hereinafter abbreviated as phenoxy resin (a)). [Abbreviated as phenoxy resin (a)] can be prepared, for example, by the following method.
1. A method for producing an epihalohydrin by reacting a bifunctional phenol having a naphthalene skeleton in the presence of an alkali (hereinafter abbreviated as a one-step method).
2.2 A method of producing by reacting a bifunctional epoxy resin having at least one of a functional epoxy resin and a bifunctional phenol having a naphthalene skeleton and a bifunctional phenol compound in the presence of a catalyst (hereinafter abbreviated as a two-step method) .

  In the said manufacturing method, the phenoxy resin (a) used for preparation of a phenoxy resin (A) is manufactured by adjusting suitably the preparation molar ratio of an epihalohydrin and a phenol compound, and the preparation molar ratio of a bifunctional epoxy resin and a bifunctional phenol compound. I can do it.

  Examples of the epihalohydrin include epichlorohydrin and epibromohydrin.

  Examples of the bifunctional phenol compound having a naphthalene skeleton include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, , 1-bi-2-naphthol and the like.

  In the one-step method, phenols other than the bifunctional phenol having the naphthalene skeleton can be used as necessary. Specifically, for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol fluorene; 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, etc. Bicyclic phenols; monocyclic bifunctional phenols such as catechol, resorcin, and hydroquinone; bisphenolacetophenone, dihydroxybiphenyl ether, dihydroxybiphenylthioether, and the like.

  The phenol compound such as a bifunctional phenol used in the present invention may be substituted with a substituent that does not have an adverse effect such as an alkyl group, an aryl group, an ether group, or an ester group. These phenol compounds can be used in combination of two or more.

  Examples of the bifunctional epoxy resin having a naphthalene skeleton include diglycidyl ether of 1,4-dihydroxynaphthalene, diglycidyl ether of 1,5-dihydroxynaphthalene, diglycidyl ether of 1,6-dihydroxynaphthalene, 2,6 -Diglycidyl ether of dihydroxynaphthalene, diglycidyl ether of 2,7-dihydroxynaphthalene, diglycidyl ether of 1,1-bi-2-naphthol, and the like.

  Examples of the bifunctional epoxy resin other than the bifunctional epoxy resin having a naphthalene skeleton include, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin; 4,4′-biphenol Diglycidyl ether, biphenol type epoxy resin such as 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol diglycidyl ether; diglycidyl monocyclic bifunctional phenol such as catechol, resorcin, hydroquinone Ethers; epoxy resins such as diglycidyl ether of bisphenolfluorene, diglycidyl ether of bisphenolacetophenone, dihydroxybiphenyl ether, diglycidyl ether of dihydroxybiphenylthioether; Epoxy resins such as diglycidyl ether of bifunctional alcohols such as rhohexanedimethanol, 1,6-hexane and neopentyl glycol; divalent carboxylic acids such as phthalic acid, isophthalic acid, tetrahydrophthalic acid and hexahydrophthalic acid Examples thereof include epoxy resins such as diglycidyl ester.

  The bifunctional epoxy resin used in the present invention may be substituted with a substituent having no adverse effect, such as an alkyl group, an aryl group, an ether group, or an ester group. These epoxy resins can be used in combination of plural kinds.

The phenoxy resin (a) used for the preparation of the phenoxy resin (A) used in the present invention may be obtained by either of the production methods 1 and 2, but the phenoxy resin obtained by the production method 2 (bifunctional epoxy resin and 2 A phenoxy resin obtained by reacting with a functional phenol compound is preferable because a phenoxy resin having a skeleton in which two or more kinds of structural units having different properties are repeatedly arranged can be easily produced.

  Among the phenoxy resins obtained by the above production method 2 as the phenoxy resin (a), an epoxy resin containing a 3,3 ′, 5,5′-tetramethylbiphenol skeleton is used as a bifunctional epoxy resin, and a naphthalene skeleton as a bifunctional phenol compound The phenoxy resin obtained using the phenol compound containing is more preferable.

  Further, when preparing the phenoxy resin (a), bisphenol S, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol, bisphenol fluorene can be used in combination as a phenol compound.

  Among the phenoxy resins obtained by the production method 2, an epoxy resin containing a 3,3 ′, 5,5′-tetramethylbiphenol skeleton as a bifunctional epoxy resin and a phenol resin containing a naphthalene skeleton as a bifunctional phenol compound are reacted. The phenoxy resin obtained in this manner is preferred because of its low dielectric constant, low dielectric loss tangent, storage stability, compatibility, solvent solubility, heat resistance, and ease of synthesis.

  In the above production method 2, a synthesis catalyst is usually used. Such a synthetic catalyst is not particularly limited as long as it has a catalytic ability to promote the etherification reaction of an epoxy group and a phenolic hydroxyl group. For example, an alkali metal compound, an organic phosphorus compound, a tertiary amine , Quaternary ammonium salts, cyclic amines, imidazoles and the like.

  Specific examples of the alkali metal compound include, for example, alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide; alkali metals such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride, and potassium chloride. Salts; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal phenoxides, alkali metal salts of organic acids such as sodium hydride, lithium hydride, sodium acetate and sodium stearate;

  Specific examples of the organic phosphorus compound include, for example, chain phosphines such as tri-n-propylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, triphenylphosphine, and diphenylmethylphosphine; Phosphines; bisphosphines such as 1,2-bis (dimethylphosphino) ethane and 1,4-bis (diphenylphosphino) butane; tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphos Phonium hydroxide, trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenyl Examples include ruphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide. It is done.

  Specific examples of the tertiary amine include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like. Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Id, and phenyl trimethylammonium chloride and the like.

  Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, benzyltributylammonium chloride, and tetrabutylammonium chloride.

  Examples of the cyclic amines include 1,8-diazabicyclo (5,4,0) undecene-7 and 1,5-diazabicyclo (4,3,0) nonene-5.

  Specific examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

  These catalysts can be used in combination. Usually, the amount of the catalyst used is preferably 0.001 to 3% by weight, more preferably 0.1 to 2% by weight, and more preferably 0.5 to 1% by weight in the reaction solid content.

  Of these, chain phosphines such as triphenylphosphine and tributylphosphine are preferable in terms of ease of synthesis and storage stability, and triphenylphosphine is more preferable.

  In addition, the phenoxy resin used in the present invention may use a solvent in the synthesis reaction during its production, and any solvent may be used as long as it dissolves the phenoxy resin. Examples include amide solvents, ketone solvents, glycol solvents, aromatic solvents, ester solvents, and other polar solvents.

  Examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N, N ′, N′-tetramethylurea. , 2-pyrrolidone, N-methylpyrrolidone, carbamic acid ester and the like.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetylacetone, diisobutyl ketone, isophorone, methylcyclohexanone, acetophenone, and the like.

  Examples of the glycol solvent include ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl. Polyethylene glycol dialkyl ethers such as ether and triethylene glycol dibutyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate;

Polyethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate; propylene glycol dimethyl ether , Propylene glycol dialkyl ethers such as propylene glycol diethyl ether and propylene glycol dibutyl ether; dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol Methyl ether, tripropylene glycol diethyl ether, polypropylene glycol dialkyl ethers such as tripropylene glycol dibutyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate; dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, Polypropylene glycol monoalkyl ether acetates such as tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate; dialkyl ether of copolymer polyether glycol such as low molecular weight ethylene-propylene copolymer Ethers; copolymerization monoacetate monoalkyl ethers polyether glycol; copolymerized alkyl esters of polyether glycol; monoalkyl esters monoalkyl ethers copolymerized polyether glycol, and the like.

  Examples of the aromatic solvent include benzene, toluene, xylene and the like, Solvesso 100 (manufactured by Kyoei Solvent Co.), Solvesso 150 (manufactured by Kyoei Solvent Co., Ltd.), and the like.

  Examples of the ester solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, and n-butyl acetate.

  Examples of the other polar solvent include dimethyl sulfoxide, sulfolane, and γ-butyrolactone.

  As a synthesis condition of the phenoxy resin in the two-stage method, the blending equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol is epoxy group / phenolic hydroxyl group = 1: 0.9 to 1.1. It is preferable that the obtained phenoxy resin has a high molecular weight in a linear form, is less susceptible to cross-linking due to side reactions, and can be easily dissolved in a solvent, and is preferably 1: 0.95 to 1: 1.05. Further preferred.

  The polymerization reaction temperature of the phenoxy resin in the two-stage method is usually within a temperature range in which the catalyst is not decomposed under a nitrogen atmosphere. The reaction temperature is preferably from 60 to 200 ° C., more preferably from 100 to 170 ° C., and even more preferably from 120 to 160 ° C. because the high molecular weight reaction proceeds favorably and side reactions do not easily occur. In addition, when using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave.

  The phenoxy resin (A) used in the present invention can be obtained, for example, by esterifying a hydroxyl group in the phenoxy resin (a). For esterification, not only direct esterification but also a method such as transesterification may be used.

  Examples of the acid component used for the esterification include acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, octanoic acid, caprylic acid, lauric acid, stearic acid, oleic acid, benzoic acid, t-butylbenzoic acid, hexahydro Organic acids such as benzoic acid, phenoxyacetic acid, acrylic acid, and methacrylic acid; acid anhydrides of organic acids; halides of organic acids; esterified products of organic acids, and the like can be used.

  Examples of the acid anhydride of the organic acid include acetic anhydride, benzoic anhydride, phenoxyacetic anhydride, and examples of the esterified product include methyl acetate, ethyl acetate, butyl acetate, methyl benzoate, and ethyl benzoate. .

  Examples of the organic acid halide include acetic acid chloride, benzoic acid chloride, phenoxyacetic acid chloride, and the like.

  Compounds used for the esterification include organic acid halides such as acetic acid chloride, benzoic acid chloride, phenoxyacetic acid chloride, acid halides such as acetic anhydride, benzoic acid anhydride, phenoxyacetic acid anhydride, and acid anhydrides of organic acid. Acidic anhydrides such as acetic anhydride and benzoic anhydride are more preferred in that they do not require washing with water after esterification and avoid the incorporation of halogens that are hated in electrical materials.

  The organic acid used for esterification of the hydroxyl group of the phenoxy resin (a); an acid anhydride of an organic acid; a halide of an organic acid; an acid component such as an esterification of an organic acid and the phenoxy resin (a) are reacted. The charge ratio at the time may be the same as the target esterification ratio, or if the reactivity is low, the acid component is charged excessively with respect to the hydroxyl group and reacted to the target esterification ratio. The acid component of the reaction may be removed.

  When esterifying directly with an acid component, various esterifications such as acid catalysts such as paratoluenesulfonic acid and phosphoric acid; metal catalysts such as tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, dioctyltin oxide, and zinc chloride It can be performed while dehydrating using a catalyst. Usually, it is preferable to carry out at 100-250 degreeC by nitrogen atmosphere, More preferably, it is 130-230 degreeC.

  When acid halides or acid anhydrides are used for esterification, in order to remove the generated acid, a method of filtering a salt after neutralization using a basic compound, a neutral compound using a basic compound, and washing with water Any of a method, a method of washing without neutralization, and a method of removing by distillation or adsorption may be used, or they may be used in combination. When removing an acid having a boiling point lower than that of the synthetic solvent, it is preferably distilled off.

  When esterifying the phenoxy resin (a) by transesterification, for example, dibutyltin oxide, dioctyltin oxide, stannoxane catalyst, tetraisopropyl titanate, tetrabutyl titanate, lead acetate, zinc acetate, antimony trioxide under a nitrogen atmosphere. It is desirable to carry out the dealcoholization using a known esterification catalyst such as an organic metal catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid, sulfonic acid or the like, or a basic catalyst such as lithium hydroxide or sodium hydroxide.

  In addition, the synthesis of the phenoxy resin (a) and the esterification of the hydroxyl group may be performed simultaneously. That is, in the above production method 2, a phenol compound that has been previously activated esterified with an acid anhydride or acid chloride is reacted with the bifunctional epoxy resin. There is no problem even if a method of esterifying simultaneously with phenoxylation is used.

  Examples of the solvent (B) used in the present invention include solvents that can be used in the preparation of the phenoxy resin (a). The solvent (B) may be the same as that used in the preparation of the phenoxy resin (a) or may be different. Moreover, you may use individually and may use 2 or more types together.

  The mixing ratio of the phenoxy resin (A) and the solvent (B) in the resin composition of the present invention is preferably 20 to 400, more preferably 100 to 250, based on 100 parts by weight of the solid content of the phenoxy resin (A). .

  If necessary, other resins, additives, thermoplastic resins other than the phenoxy resin (A), and the like can be added to the resin composition of the present invention.

  Examples of the other resin include epoxy resin, phenol resin, polyurethane resin, imide resin, amino resin, melamine resin, alkyd resin, unsaturated polyester resin, acrylic resin, unsaturated polyester resin, xylene resin, silicon resin, fluorine Examples thereof include resins.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, bisphenol S type epoxy resin, alkylphenol novolac type epoxy resin, biphenol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type. Epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having a phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resins, etc., and epoxy resins having two or more epoxy groups in one molecule Can be mentioned. Moreover, an epoxy resin modified with chlorine, bromine, phosphorus, sulfur, nitrogen or the like to impart flame retardancy may be used.

  The epoxy resin is preferably an aromatic epoxy resin having an aromatic ring skeleton in the molecule. The epoxy resin may be either an epoxy resin that is solid at normal temperature or an epoxy resin that is liquid at normal temperature.

  When adding an epoxy resin to the resin composition of this invention, the hardening | curing agent hardening | curing agent and catalyst of an epoxy resin can be used together as needed.

  As the curing agent for the epoxy resin, for example, phenol-based curing agents, acid anhydride-based curing agents, amines, polyamide resins, isocyanate resins or derivatives thereof may be used as well as known ones or in combination of two or more. You can also.

  Examples of the phenolic curing agent include phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, cresol novolac resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene modified phenol resin, polyvinylphenols, naphthalene type phenols. A well-known and customary thing can be used individually or in combination of 2 or more types. Furthermore, a phenol type hardening | curing agent can also contain a nitrogen atom. Use of a phenolic curing agent improves flame retardancy and adhesion. Examples of the phenolic curing agent having a nitrogen atom include a triazine structure-containing novolak resin, Phenolite 7050 series manufactured by Dainippon Ink & Chemicals, Inc., and Melamine-modified phenol novolak resin manufactured by Yuka Shell. About the compounding quantity of said phenol resin, it is desirable to mix | blend the phenol resin of 0.5-1.3 phenolic hydroxyl group equivalent with respect to 1 epoxy equivalent epoxy resin.

  Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, neglected benzophenone tetracarboxylic acid, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, etc. Cyclic aromatic anhydrides, negligible maleic acid, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Known and commonly used ones such as neglected aliphatic acids, aliphatic acid anhydrides and halogenated anhydrides can be used alone or in combination of two or more.

  Examples of the curing agent for the amines include aliphatic polyamines such as diethylenetriamine, triethylenetriamine, N-aminoethylpiperazine, isophoronediamine, xylenediamine, and xylenediamine trimer, metaphenylenediamine, diaminodiphenylmethane, and diamino. Aromatic amines such as diphenylsulfone, polyamine epoxy resin adducts, polyamine-ethylene oxide adducts, polyamine-propylene oxide adducts, modified amines such as cyanoethylated polyamines and ketimines, secondary amines such as piperidine, etc. It can be used alone or in combination of two or more.

  Examples of the polyamide resin-based curing agent include, in addition to polyamide resins obtained by reacting dimer acid and diamine, known and commonly used ones such as modified polyamide resins modified with an epoxy resin, Mannich-type polyamide resins, and the like. It can be used in combination of more than one species.

The imide resin curing agent is, for example, an imide resin having a functional group reactive with an epoxy group such as a carboxylic acid group, a phenolic hydroxyl group, an isocyanate group, or an amino group,
Those having an isocyanurate skeleton are preferred, and those having a carboxylic acid group, an acid anhydride group, and a phenolic hydroxyl group are more preferred as the functional group.

  In the case of using the epoxy resin, examples of the curing catalyst that can be used as needed include tertiary amines such as DBU, guanidines, 2-methylimidazole, 2-ethyl-4-methylimidazole, Imidazoles such as 2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis (hydroxymethyl) imidazole, triphenylphosphine, tributylphosphine, tetraphenylphosphonium It is also possible to use known or conventional compounds such as organophosphorus compounds or derivatives thereof such as those encapsulated therein, or a combination of two or more thereof.

  Examples of the various additives include thickeners such as asbestos, olben, and benton; silicone-based antifoaming agents, fluorine-based antifoaming agents, polymer-based antifoaming agents and / or leveling agents; imidazole-based, thiazole-based, Adhesion imparting agents such as triazole, silane coupling agents; inorganic fillers such as calcium carbonate, magnesium carbonate, magnesium oxide, aluminum hydroxide, barium sulfate, barium titanate, silicon oxide powder, amorphous silica, talc, clay, mica Kinds: Fillers such as acrylic fine particles, nylon fine particles, silicone fine particles, fluorine fine particles, organic fillers obtained by thermosetting and finely pulverizing amino resins; copper phthalocyanine-type such as phthalocyanine blue, phthalocyanine green, quinacridone type, chrome lead, Like zinc chromate, molybdate orange Chromate, ferrocyanide such as bitumen, titanium oxide, zinc white, bengara, iron oxide, metal oxide such as chromium carbide green, metal sulfide such as cadmium yellow, cadmium red, mercury sulfide, selenide, lead sulfate Sulfates such as ultramarine, silicates such as ultramarine, carbonates, cobalt biored, phosphates such as manganese purple, metal powders such as aluminum powder, zinc dust, brass powder, magnesium powder, iron powder, copper powder, nickel powder In addition to pigments such as carbon black, phosphorus-based flame retardants, stabilizers, ultraviolet absorbers, silicates, chelating agents, and the like can be used as necessary.

  Examples of the thermoplastic resin other than the phenoxy resin (A) include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene resin, acrylonitrile / butadiene / styrene resin, methacrylic resin, vinyl chloride, polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate. , Polymethylpentene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, polytetrafluoroethylene, polyetherimide, polyarylate, polysulfone, polyethersulfone, polyamideimide, chlorinated polyolefin, petroleum resin, Examples thereof include nitrocellulose.

  Next, the phenoxy resin of the present invention will be described. The phenoxy resin of the present invention is characterized by having a structure represented by the following general formula (1) and having a weight average molecular weight of 5,000 to 200,000.

（式中、Ａは、水素原子または下記一般式（２）で表される基である。また、Ｒ_１は炭素原子数１〜２０の炭化水素基を有するアシル基で、ａは２０以上である。）

(In the formula, A is a hydrogen atom or a group represented by the following general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a is 20 or more. is there.)

In the phenoxy resin (A) used in the present invention, R ₁ (a structure in which hydroxyl groups are bonded by esterification) has excellent dielectric properties and good compatibility with other resins, and therefore has polar groups such as hydroxyl groups and carboxylic acids. None is preferred. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, i-butyl group, t-butyl group, vinyl group, and benzyl group. , A naphthyl group and a phenethyl group are preferred. Among them, an acyl group having a hydrocarbon group having 1 to 6 carbon atoms is more preferable, a methyl group or a benzyl group is more preferable, and a methyl group is still more preferable.

  When the weight average molecular weight of the phenoxy resin of the present invention is less than 5,000, it is not preferable because the film forming property and mechanical properties are deteriorated. When the weight average molecular weight is larger than 200,000, it is not preferable because the compatibility is lowered. Therefore, the weight average molecular weight is preferably 5,000 to 200,000, and more preferably 10,000 to 100,000.

Moreover, although the repeating unit (a) in the said General formula (1) should just be 20 or more, 20-800 are preferable from the reason of film forming property, mechanical physical property, and compatibility, and 40-400 are more preferable.

  The phenoxy resin of the present invention only needs to have the structure represented by the general formula (1). Among these, the naphthalene skeleton structure may contain 10 to 60% by weight based on the weight of the phenoxy resin (A). It is preferable from the viewpoint of excellent heat resistance and compatibility, and a phenoxy resin containing 15 to 55% by weight is more preferable.

  Among the phenoxy resins of the present invention, among them, a phenoxy resin containing a structure represented by the following general formula (3) is preferable because of excellent heat resistance, compatibility, and dielectric properties.

〔式中、Ａは、水素原子または上記一般式（２）で表される基である。また、Ｒ_１は炭素原子数１〜２０の炭化水素基を有するアシル基で、Ｂは炭素原子数１〜３０の炭化水素である。また、ａ１は２０〜８００である。〕

[Wherein, A represents a hydrogen atom or a group represented by the general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and B is a hydrocarbon having 1 to 30 carbon atoms. Moreover, a1 is 20-800. ]

  Examples of the hydrocarbon having 1 to 30 carbon atoms include a residue obtained by removing two hydrogens from methane, a residue obtained by removing two hydrogens from ethane, a residue obtained by removing two hydrogens from propane, and hexane. Residues with 2 hydrogens removed, residues with 2 hydrogens removed from cyclohexane, residues with 2 hydrogens removed from benzene, residues with 2 hydrogens removed from diethylene glycol, 2 hydrogens from triethylene glycol Residues removed, residues obtained by removing two hydrogens from dipropylene glycol, residues obtained by removing two hydrogens from tripropylene glycol, residues obtained by removing two hydrogens from hydrogenated bisphenol A, hydrogenated bisphenols Residue obtained by removing two hydrogens from F, residue obtained by removing two hydrogens from hydrogenated bisphenol S, residue obtained by removing two hydrogens from hydrogenated biphenol, hydrogenated tetra Residues obtained by removing two hydrogens from tilbiphenol, residues obtained by removing two hydrogens from dicyclopentadienediol, residues obtained by removing two hydrogens from dibromoneopentyl alcohol, 2- (9 ′, 10′-dihydro- Residues obtained by removing two hydroxyl groups from 9′-phosphate 9′-oxide-10′-oxaphenanthrene-9′-yl) -1,4-dihydrobenzene (Sanko Chemical Co., Ltd. HCA-HQ) It is done.

  In the present invention, the hydrocarbon or hydrocarbon group can be used as a hydrocarbon or hydrocarbon group even if it contains a hetero atom, a halogen atom, an oxygen atom, a sulfur atom, a carbonyl group or the like.

  Among the hydrocarbons having 1 to 30 carbon atoms, a phenoxy resin having a structure represented by the following general formula (4) is more preferable.

〔式中、Ｒ_２〜Ｒ_９は同一でも異なっていても良く、それぞれ水素原子、メチル基またはハロゲン原子を示す。Ｒ_１０は直接結合、炭素原子数１〜１８の炭化水素構造、スルホニル基（ＳＯ_２）、カルボニル基（ＣＯ）、酸素原子（Ｏ）、硫黄原子（Ｓ）および下記一般式（５）からなる群から選ばれる一種以上の構造である。〕

[Wherein, R _{2 to} R ₉ may be the same or different and each represents a hydrogen atom, a methyl group or a halogen atom. R ₁₀ comprises a direct bond, a hydrocarbon structure having 1 to 18 carbon atoms, a sulfonyl group (SO ₂ ), a carbonyl group (CO), an oxygen atom (O), a sulfur atom (S), and the following general formula (5). One or more structures selected from the group. ]

（式中、Ｒ_１１〜Ｒ_１８は同一でも異なっていても良く、それぞれ水素原子またはメチル基を示す。）

(In the formula, R _{11 to} R ₁₈ may be the same or different and each represents a hydrogen atom or a methyl group.)

The _{R 1} in the general formula (3), for example, _{R 1} or the like in the general formula (1).

  Examples of the structure of the general formula (4) include a residue obtained by removing two hydrogens from biphenol, a residue obtained by removing two hydrogens from dimethyl-4,4′-biphenol, 3,3 ′, 5,5 ′. A residue obtained by removing two hydrogens from tetramethyl-4,4′-biphenol, a residue obtained by removing two hydrogens from bisphenol S, a residue obtained by removing two hydrogens from 4,4′-oxybisphenol, 4 , 4′-thiobisphenol, a residue obtained by removing two hydrogens, a residue obtained by removing two hydrogens from bis (4-hydroxyphenyl) methanone, a residue obtained by removing two hydrogens from bisphenol A, and a residue obtained by removing bisphenol B from 2 Residues obtained by removing two hydrogens from bisphenol C, residues obtained by removing two hydrogens from bisphenol F, residues obtained by removing two hydrogens from bisphenol Z, Residues obtained by removing two hydrogens from dichlorobisphenol A, residues obtained by removing two hydrogens from dibromobisphenol A, residues obtained by removing two hydrogens from dichlorobiphenol, residues obtained by removing two hydrogens from dibromobisphenol, etc. Is mentioned. Among them, residues obtained by removing two hydrogens from 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, residues obtained by removing two hydrogens from bisphenol S, and 4,4′-oxybisphenol Residues obtained by removing two hydrogens, residues obtained by removing two hydrogens from 4,4′-thiobisphenol, and residues obtained by removing two hydrogens from bis (4-hydroxyphenyl) methanone are preferred. Residues obtained by removing two hydrogens from ', 5,5'-tetramethyl-4,4'-biphenol and residues obtained by removing two hydrogens from bisphenol S are preferred.

The phenoxy resin of the present invention is preferable because a phenoxy resin having a structure represented by the following general formula (6) and the following general formula (7) is excellent in heat resistance, dielectric properties, and compatibility.

〔式中、Ａは、水素原子または上記一般式（２）で表される基である。また、Ｒ_１は炭素原子数１〜２０の炭化水素基を有するアシル基で、ａ２は２０〜８００である。〕

[Wherein, A represents a hydrogen atom or a group represented by the general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a2 is 20 to 800. ]

〔式中、Ａは、水素原子または上記一般式（２）で表される基である。また、Ｒ_１は炭素原子数１〜２０の炭化水素基を有するアシル基で、ａ３は２０〜８００である。〕

[Wherein, A represents a hydrogen atom or a group represented by the general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a3 is 20 to 800. ]

The R ₁ in the general formula (6) and the following general formula (7), for example, R _1, and the like represented by the general formula (1).

  The phenoxy resin of the present invention can be produced by, for example, a production method used for preparing the phenoxy resin (A) used in the resin composition of the present invention.

  The paint adhesive composition of the present invention may contain the resin composition of the present invention as an essential component, and if necessary, various additives, solvents, thermoplastic resins other than the phenoxy resin (A), and the like. Can be added.

  The adhesive composition of the present invention may contain the resin composition of the present invention as an essential component, and if necessary, various additives, solvents, thermoplastic resins other than the phenoxy resin (A), and the like are added. can do.

  The adhesive film of the present invention is obtained by forming a thin film of the resin composition of the present invention on a support base film. As a manufacturing method, a support base film is used as a support, and after applying the resin composition of the present invention to the surface thereof, the solvent is dried by heating and / or hot air blowing to form a thin film, thereby producing an adhesive film.

  Examples of the supporting base film include polyolefins such as polyethylene and polyvinyl chloride, polyesters such as polyethylene terephthalate, polycarbonates and polyimides, and metal foils such as release paper, copper foil, and aluminum foil. Note that the support base film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  The prepreg of the present invention can be prepared by applying the resin composition of the present invention to a sheet-like reinforcing base material comprising fibers by a hot melt method or a solvent method, impregnating, heating and semi-curing. As the sheet-like reinforcing substrate made of fibers, known and commonly used prepreg fibers such as glass cloth and aramid fibers can be used. In the hot melt method, a solvent-free resin is used, and a method of coating the resin once with a resin having good releasability and laminating it, or directly coating with a die coater is known. The solvent method is a method of obtaining a prepreg by immersing and impregnating a sheet-like reinforcing base material in an organic solvent in the same manner as an adhesive film, and then drying it.

In the multilayer printed wiring board of the present invention, a plated conductor layer is formed on a cured product obtained by curing the resin composition of the present invention, and the other surface is laminated in close contact with the patterned internal circuit board. The multilayer printed wiring board of the present invention is produced by laminating an adhesive film made of the resin composition of the present invention on a patterned inner layer circuit board. When the protective film is present, the laminate is bonded after applying pressure and heating to the thin film of the resin composition of the present invention having adhesive performance after removing the protective film. As for the lamination conditions, it is preferable that the film and the inner layer circuit board are preheated as necessary, the pressure bonding temperature is 70 to 130 ° C., the pressure bonding pressure is 1 to 11 Kgf / cm ² , and the layers are laminated under reduced pressure. Further, the laminate may be a batch type or a continuous type using a roll. After lamination, the support film is peeled off after cooling to around room temperature, the resin composition is transferred onto the inner layer circuit board, and then cured by heating. Moreover, when using the support film in which the mold release process was performed, you may peel a support film, after making it heat-harden. Thereafter, as in the above method, the surface of the film is roughened with an oxidizing agent, and the conductor layer is formed by plating to produce a multilayer printed wiring board.

On the other hand, in order to produce a multilayer printed wiring board using the prepreg comprising the resin composition of the present invention, one or several sheets of the prepreg are stacked on a patterned inner layer circuit board, and a release film is interposed therebetween. The metal plate is sandwiched and pressed under pressure and heating conditions. The pressure condition is preferably 5 to 40 kgf / cm ² , and the temperature condition is preferably 120 to 180 ° C. for 20 to 100 minutes. It can also be manufactured by the laminating method. Thereafter, as in the above method, the surface of the prepreg is roughened with an oxidizing agent, and the conductor layer is formed by plating to produce a multilayer printed wiring board. The manufactured multilayer printed wiring board has an insulating layer that is a cured product of the resin composition between the inner-layer circuits when the inner-layer circuit board has two or more inner-layer circuits patterned in the same direction. become. The patterned inner layer circuit board referred to in the present invention is a relative name to the multilayer printed wiring board. For example, a four-layer printed wiring board can be formed by forming circuits on both sides of a substrate and forming a thin film of a cured resin composition on both circuit surfaces as an insulating layer and then forming circuits on both surfaces. In this case, the inner layer circuit board refers to a printed wiring board having circuits formed on both sides formed on the board. Further, a six-layer printed wiring board can be obtained by additionally forming a single-layer circuit on both surfaces of the four-layer printed wiring board via an insulating layer. The inner layer circuit board in this case refers to the above-described four-layer printed wiring board.

  Specifically, for example, the thickness of the resin composition layer is equal to or greater than the conductor thickness of the inner circuit board to be laminated on the support base film having a thickness of 10 to 200 μm, and is in the range of 10 to 150 μm. A protective film such as a support film having a thickness of 1 to 40 μm is further laminated and stored in a roll shape.

  Next, the present invention will be described more specifically with reference to examples and comparative examples. Unless otherwise indicated, “parts” and “%” are based on weight.

Synthesis Example 1 (Production of hydroxyl group-containing phenoxy resin)
In a flask equipped with a stirrer, a thermometer and a condenser, Epiklon HP4032D (Naphthalene type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc.) 100 g (0.355 mol) and dihydroxynaphthalene 55.6 g (0.348 mol) 233.4 g of cyclohexanone was charged, heated to 80 ° C. while paying attention to heat generation while blowing nitrogen and stirring, and then added 1.55 g of triphenylphosphine as a reaction catalyst, and further heated to 150 ° C. over 1 hour. The mixture was reacted at 150 ° C. for 3 hours until the solid equivalent epoxy equivalent reached 10,000. By this reaction, a resin solution (a1) containing a naphthalene / naphthalene phenoxy resin having a secondary hydroxyl group was obtained (nonvolatile content: 40%).

  The obtained naphthalene / naphthalene-based phenoxy resin has an epoxy equivalent (solid conversion) of 10000, and when measured by gel permeation chromatography (GPC), the resin has a weight average molecular weight (Mw) of 36000. When the ratio of the phenolic compound is 2% or less and the infrared absorption spectrum is measured, the characteristic absorption of the epoxy group near 915 cm-1 decreases, and the broad characteristic absorption of the secondary hydroxyl group generated by the reaction between the epoxy and phenol (3450 cm-1 It was concluded that a phenoxy resin having a secondary hydroxyl group was obtained.

Synthesis example 2 (same as above)
To a flask equipped with a stirrer, a thermometer and a condenser, Epicoat YX4000H (3,3 ′, 5,5′-tetramethylbiphenyl type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd.) 100 g (0.259 mol) and dihydroxynaphthalene 40.6 g (0.254 mol) and cyclohexanone 210.9 g were charged and heated to 80 ° C. while paying attention to heat generation while blowing nitrogen and stirring, and 1.41 g of triphenylphosphine was added as a reaction catalyst. After heating up to 150 degreeC over time, it was made to react at 150 degreeC for 6 hours. By this reaction, a resin solution (a2) containing a 3,3 ′, 5,5′-tetramethylbiphenyl / naphthalene phenoxy resin having a secondary hydroxyl group was obtained (nonvolatile content: 40%).

  The obtained 3,3 ′, 5,5′-tetramethylbiphenyl / naphthalene-based phenoxy resin has an epoxy equivalent (solid equivalent) of 8000, and when measured by GPC, the weight average molecular weight (Mw) of the resin is 44,000. When the ratio of the raw material epoxy resin and phenolic compound is 2% or less and the infrared absorption spectrum is measured, the characteristic absorption of the epoxy group near 915 cm-1 decreases, and the broad characteristic of the secondary hydroxyl group generated by the reaction between the epoxy and phenol It is concluded that the absorption (3450 cm-1) was confirmed to obtain a phenoxy resin having a secondary hydroxyl group.

Synthesis example 3 (same as above)
A flask equipped with a stirrer, a thermometer and a condenser was charged with 100 g (0.355 mol) of epiclone HP4032D and 88.7 g (0.355 mol) of bisphenol S as naphthalene epoxy resin and 283.1 g of cyclohexanone, and nitrogen was blown into the flask. While stirring, the temperature was raised to 80 ° C. while paying attention to heat generation, 1.89 g of triphenylphosphine was added as a reaction catalyst, and the temperature was further raised to 150 ° C. over 1 hour, followed by reaction at 150 ° C. for 8 hours. By this reaction, a resin solution (a3) containing a naphthalene / bisphenol S phenoxy resin having a secondary hydroxyl group was obtained (nonvolatile content: 40%).

  The obtained naphthalene / bisphenol S-based phenoxy resin has an epoxy equivalent (solid conversion) of 100,000. When GPC is measured, the weight average molecular weight (Mw) of the resin is 18,000, and the ratio of the raw material epoxy resin and phenol compound is 2. When the infrared absorption spectrum was measured, the characteristic absorption of the epoxy group in the vicinity of 915 cm-1 decreased, and the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group caused by the reaction between the epoxy and phenol was confirmed. Thus, it is concluded that a phenoxy resin having a secondary hydroxyl group was obtained.

Synthesis Example 4 (Production of hydroxyl group-containing phenoxy resin for comparison)
A flask equipped with a stirrer, a thermometer and a condenser was charged with 100 g (0.259 mol) of Epicoat YX4000H, 63.9 g (0.256 mol) of bisphenol S, and 245.9 g of cyclohexanone. Carefully, the temperature was raised to 80 ° C., 3.27 g of triphenylphosphine was added as a reaction catalyst, and the temperature was further raised to 150 ° C. over 1 hour, followed by reaction at 150 ° C. for 6 hours. By this reaction, a resin solution (a′1) containing a tetramethylbiphenyl / bisphenol S-based phenoxy resin having a secondary hydroxyl group was obtained (nonvolatile content: 40%).

  The obtained tetramethylbiphenyl / bisphenol S-based phenoxy resin has an epoxy equivalent (solid conversion) of 30000. When GPC is measured, the weight average molecular weight (Mw) of the resin is 50000, and the ratio of the raw material epoxy resin and phenol compound When the infrared absorption spectrum was measured, the characteristic absorption of the epoxy group in the vicinity of 915 cm-1 decreased, and the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group caused by the reaction between the epoxy and phenol was confirmed. It is concluded that a phenoxy resin having a secondary hydroxyl group was obtained.

Synthesis example 5 (same as above)
In a flask equipped with a stirrer, a thermometer and a condenser, Epiklon 850S (bisphenol A type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc.) 100 g (0.266 mol) and bisphenol A 59.9 g (0.263 mol) And 68.5 g of cyclohexanone were added, and heated to 80 ° C. while paying attention to heat generation while blowing nitrogen and stirring, and then charged with 3.20 g of triphenylphosphine as a reaction catalyst, and further heated to 150 ° C. over 1 hour. Then, it was made to react at 150 degreeC for 6 hours. By this reaction, a resin solution (a′2) containing a bisphenol A / bisphenol A phenoxy resin having a secondary hydroxyl group was obtained (nonvolatile content: 70%).

  The epoxy equivalent (solid conversion) of the obtained bisphenol A / bisphenol A-based phenoxy resin is 10,000. When GPC is measured, the weight average molecular weight (Mw) of the resin is 17000, and the ratio of the raw material epoxy resin and phenol compound is When the infrared absorption spectrum was measured, the characteristic absorption of the epoxy group in the vicinity of 915 cm-1 decreased, and the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group caused by the reaction between the epoxy and phenol was confirmed. It is concluded that a phenoxy resin having a secondary hydroxyl group was obtained.

Synthesis Example 6 [Production of Phenoxy Resin (A)]
A flask equipped with a stirrer, a thermometer, and a distillation apparatus was charged with 39.4 g of acetic anhydride in an amount that acetylates 50% of the hydroxyl group in the phenoxy resin solution (a1), reacted at 120 ° C. for 2 hours, and then released. In order to remove acetic acid, heating was performed while appropriately raising the temperature between 130 to 160 ° C., and acetic acid was removed together with cyclohexanone. Deacetic acid was performed so that the acid value in the flask was 5 or less while cyclohexanone was added. . Finally, an acetylated phenoxy resin solution (A1) having an acid value of 1.2, a nonvolatile content of 35.0%, and a viscosity of 10.0 Pa · s was obtained.

  When the GPC of the obtained phenoxy resin was measured, the weight average molecular weight (Mw) of the resin was 38000, and the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group was reduced, so that the secondary hydroxyl group was acetylated. It is concluded that a resin was obtained.

Synthesis example 7 (same as above)
A flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 70.9 g of acetic anhydride in an amount for acetylating 90% of the hydroxyl groups in the phenoxy resin solution (a1), reacted at 120 ° C. for 2 hours, and then released. In order to remove acetic acid, heat the mixture while raising the temperature appropriately between 130 ° C and 160 ° C and start removing acetic acid together with cyclohexanone. Deacetic acid is performed so that the acid value in the flask is 5 or less while adding cyclohexanone. It was. Finally, an acetylated phenoxy resin solution (A2) having an acid value of 1.2, a nonvolatile content of 34.3%, and a weight average molecular weight (Mw) of 39000 was obtained.

  When GPC of the obtained phenoxy resin was measured, it was concluded that a phenoxy resin in which the secondary hydroxyl group was acetylated was obtained because the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group was reduced.

Synthesis example 8 (same as above)
A flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 86.7 g of acetic anhydride having a 1.1-fold excess equivalent in order to acetylate 100% of the hydroxyl group into the obtained phenoxy resin solution (a1). After reacting at 2 ° C. for 2 hours, in order to remove the free acid, it was heated while appropriately raising between 130 ° C. and 160 ° C. and began to remove the acid together with cyclohexanone. Deacetic acid was performed so as to be 5 or less. Finally, an acetylated phenoxy resin solution (A3) having an acid value of 1.0, a nonvolatile content of 35.1%, a viscosity of 9.0 Pa · s, and a weight average molecular weight (Mw) of 40000 was obtained.

  When GPC of the obtained phenoxy resin was measured, it was concluded that a phenoxy resin in which the secondary hydroxyl group was acetylated was obtained because the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group was reduced.

Synthesis example 9 (same as above)
A flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 70.9 g of acetic anhydride in an amount for acetylating 90% of the hydroxyl groups in the obtained phenoxy resin solution (a2) and reacted at 120 ° C. for 2 hours. Then, in order to remove free acetic acid, it is heated while being appropriately raised between 130 ° C. and 160 ° C. to start removing acetic acid together with cyclohexanone, and removed while adding cyclohexanone so that the acid value in the flask becomes 5 or less. Acetic acid was performed. Finally, an acetylated phenoxy resin solution (A4) having an acid value of 1.4, a nonvolatile content of 29.1%, a viscosity of 2.9 Pa · s, and a weight average molecular weight (Mw) of 58000 was obtained.

  When GPC of the obtained phenoxy resin was measured, it was concluded that a phenoxy resin in which the secondary hydroxyl group was acetylated was obtained because the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group was reduced.

Synthesis example 10 (same as above)
A flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 70.9 g of acetic anhydride in an amount for acetylating 90% of the hydroxyl groups in the obtained phenoxy resin solution (a3) and reacted at 120 ° C. for 2 hours. Then, in order to remove free acetic acid, it is heated while being appropriately raised between 130 ° C. and 160 ° C. to start removing acetic acid together with cyclohexanone, and removed while adding cyclohexanone so that the acid value in the flask becomes 5 or less. Acetic acid was performed. Finally, an acetylated phenoxy resin solution (A5) having an acid value of 2.2, a non-volatile content of 34.5%, a viscosity of 1.6 Pa · s, and a weight average molecular weight (Mw) of 21,000 was obtained.

  When GPC of the obtained phenoxy resin was measured, it was concluded that a phenoxy resin in which the secondary hydroxyl group was acetylated was obtained because the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group was reduced.

Synthesis Example 11 [Production of Comparative Phenoxy Resin (A ′)]
A flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 70.9 g of acetic anhydride in an amount for acetylating 90% of the hydroxyl group to the obtained phenoxy resin solution (a′1), and reacted at 120 ° C. for 2 hours. Then, in order to remove free acetic acid, it is heated while appropriately raising between 130 ° C. and 160 ° C., and acetic acid is started to be removed together with cyclohexanone, so that the acid value in the flask becomes 5 or less while cyclohexanone is added. The acetic acid was removed. Finally, an acetylated phenoxy resin solution for comparison (A′1) having an acid value of 3.1, a nonvolatile content of 29.7%, a viscosity of 3.9 Pa · s, and a weight average molecular weight (Mw) of 54,000 was obtained.

  When GPC of the obtained phenoxy resin was measured, it was concluded that a phenoxy resin in which the secondary hydroxyl group was acetylated was obtained because the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group was reduced.

Synthesis example 12 (same as above)
A flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 70.9 g of acetic anhydride in an amount to acetylate 90% of the hydroxyl group in the obtained phenoxy resin solution (a′2), and reacted at 120 ° C. for 2 hours. Then, in order to remove free acetic acid, it is heated while appropriately raising between 130 ° C. and 160 ° C., and acetic acid is started to be removed together with cyclohexanone, so that the acid value in the flask becomes 5 or less while cyclohexanone is added. The acetic acid was removed. Finally, an acetylated phenoxy resin solution for comparison (A′2) having an acid value of 1.4, a nonvolatile content of 39.9%, a viscosity of 2.0 Pa · s, and a weight average molecular weight (Mw) of 20000 was obtained.

  When GPC of the obtained phenoxy resin was measured, it was concluded that a phenoxy resin in which the secondary hydroxyl group was acetylated was obtained because the broad characteristic absorption (3450 cm-1) of the secondary hydroxyl group was reduced.

  Tables 1 and 2 show various physical properties of the phenoxy resins obtained in Synthesis Examples 1 to 5 and the acetylated phenoxy resins obtained in Synthesis Examples 6 to 12. Moreover, the heat resistance test of the phenoxy resin and acetylated phenoxy resin obtained by these synthesis examples 1-12 was done, and these results are shown according to Table 1 and Table 2. In addition, the evaluation method of heat resistance is as follows.

<Method for evaluating heat resistance of phenoxy resin and acetylated phenoxy resin. >
-Preparation method of measurement sample The phenoxy resin solution was coated on a tin plate so that the film thickness after drying was 50 μm, dried for 1 hour with a dryer at 150 ° C., cooled to room temperature, and then the dried coating film was tinplate. A sample was cut from the plate.

-Measurement of heat resistance It evaluated by measuring a glass transition point (Tg) with a differential scanning calorimeter (DSC). It represents that the coating film which is excellent in heat resistance is obtained, so that Tg is high.

Example 1
26.7 parts of phenoxy resin solution (A1) adjusted to 30% non-volatile content with cyclohexanone, Solvesso 150 solution (70% non-volatile content) of EPICLONN-680 (Cresol novolac type epoxy resin manufactured by Dainippon Ink & Chemicals, Inc.) ) 30.7 parts, 15.0 parts of cyclohexanone solution (70% non-volatile content) of Phenolite TD-2090 (Phenol novolac type phenol resin manufactured by Dainippon Ink and Chemicals, Inc.), Curesol 2E4MZ (manufactured by Shikoku Kasei Co., Ltd.) 2.0 parts of a cyclohexanone 10% solution of 2-ethyl-4-methylimidazole) was added to a glass bottle and mixed by stirring to obtain a resin composition 1 of the present invention.

  The compatibility of the obtained composition 1 with other resins, heat resistance, and electrical characteristics were evaluated according to the following methods. The results are shown in Table 3.

(1) Evaluation method of compatibility with other resins After leaving the resin composition 1 at 25 ° C. for 5 minutes, the resin composition 1 was visually observed, and the state was evaluated according to the following criteria.
○: Solution is clear ×: Solution is cloudy or separated

(2) Heat resistance evaluation method-Preparation of sample After coating resin composition 1 on a tin plate so that the film thickness after drying is 50 µm, after drying for 1 hour with a dryer at 150 ° C and cooling to room temperature The dried coating film was cut out from the tin plate and used as a sample.
-Measurement of heat resistance It evaluated by measuring a glass transition point (Tg) by dynamic viscoelasticity (DMA). It represents that the coating film which is excellent in heat resistance is obtained, so that Tg is high.

(3) Dielectric property evaluation method The dielectric constant (ε) and dielectric loss (Tanδ) of the sample obtained in (2) above were measured using 4291B manufactured by Agilent Technologies under the condition of a frequency of 500 MHz. The lower the value, the better the dielectric properties.

Examples 2-5 and Comparative Examples 1-7
Resin compositions 1 to 5 and comparative control resin compositions 1 'to 7' were prepared in the same manner as in Example 1 except that the formulations shown in Tables 3 and 4 were used. In the same manner as in Example 1, the compatibility with other resins, heat resistance, and electrical characteristics were evaluated. The evaluation results are shown in Tables 3 and 4.

  As is apparent from the results in Table 3, in the phenoxy resin compositions of Examples 1 to 5, the phenoxy resin and the other resin have good compatibility, and the cured coating film has excellent heat resistance and dielectric constant and dielectric loss tangent. The result was low and very good dielectric properties.

  On the other hand, as is clear from the results of Tables 4 and 5, the phenoxy resin compositions of Comparative Examples 1 to 6 have poor compatibility compared to the Examples, and the dielectrics of the cured coating films of Comparative Examples 1 to 4 and 6 The rate and dielectric loss tangent were high, and the results were poor compared to the examples. Comparative Examples 6 and 7 were inferior in heat resistance compared to the examples.

Example 6
Cyclohexanone was added as a solvent to the phenoxy resin solution (A1) to obtain a resin composition 6 having a nonvolatile content of 30%. The solubility, bending resistance, heat resistance and electrical properties of the obtained composition 6 were evaluated according to the following methods. The results are shown in Table 6.

(1) Method for evaluating solubility Add 10.0 g of resin composition 6 and 10.0 g of toluene to a 100 ml Erlenmeyer flask, stir well with a glass rod, and let stand at 25 ° C. for 5 minutes, then visually observe the solution state. did. Observation was placed on a printed matter (type 10 points), viewed from above, judged whether the type could be read through the liquid layer of the Erlenmeyer flask, and evaluated according to the following criteria.
○: The solution is transparent and the printed type can be read. Δ: The solution is cloudy but the printed type can be read. ×: The solution is separated or cloudy and the printed type cannot be read.

(2) Bending resistance evaluation method The resin composition 6 was coated on a polyester film so that the film thickness after drying was 50 μm, dried in a dryer at 150 ° C. for 1 hour, cooled to room temperature, and coated. Got. This coating film was evaluated according to the following criteria.
○: The coating film does not break when it is bent 180 degrees with the coating surface facing up.
X: A crack can be confirmed in the coating film when it is bent 180 degrees with the coating film surface facing up.

(3) Heat resistance evaluation method-Preparation of sample After coating resin composition 1 on a tin plate so that the film thickness after drying is 50 µm, after drying for 1 hour with a dryer at 150 ° C and cooling to room temperature The dried coating film was cut out from the tin plate and used as a sample.
-Measurement of heat resistance It evaluated by measuring a glass transition point (Tg) with a differential operation calorimeter (DSC). It represents that the coating film which is excellent in heat resistance is obtained, so that Tg is high, the thing whose Tg is 100 or more is (circle), and the thing whose Tg is less than 100 degreeC was set as x.

(4) Evaluation Method of Dielectric Properties The dielectric constant (ε) and dielectric loss (Tanδ) of the sample obtained in (3) above were measured using 4291B manufactured by Agilent Technologies under the condition of a frequency of 500 MHz. The lower the value, the better the dielectric properties.

Examples 7 to 10 and Comparative Examples 8 to 14
Resin compositions 6 to 10 and comparative control resin compositions 8 ′ to 14 ′ were prepared in the same manner as in Example 6 except that the phenoxy resin solutions shown in Tables 6 to 8 were used. Evaluation was performed in the same manner as in Example 6, and the results are shown in Tables 6-7.

  As is apparent from the results in Table 6, in the phenoxy resin compositions of Examples 6 to 10, the phenoxy resin and the solvent toluene have good solubility, and the dried coating film has excellent heat resistance and low dielectric constant and dielectric loss tangent. The result was very good characteristics.

  On the other hand, as is clear from the results of Tables 7 and 8, the phenoxy resin compositions of Comparative Examples 8 to 13 have poor solubility compared to the Examples, and Comparative Examples 8 to 12 are bending resistant. The dried coating films 8 to 11 and 13 had high dielectric constants and dielectric loss tangents, which were bad results compared to the examples. Comparative Examples 13 and 14 were inferior in heat resistance compared to the examples.

Claims (20)

  A resin composition comprising a phenoxy resin (A) having a structure in which a naphthalene skeleton and a hydrogen atom of a hydroxyl group are substituted with an acyl group and having a weight average molecular weight of 5,000 to 200,000, and a solvent (B) object.   2. The resin composition according to claim 1, wherein the phenoxy resin (A) is a phenoxy resin having a ratio of hydroxyl group hydrogen atoms substituted with acyl groups of 10 to 100 mol%.   The resin composition according to claim 1, wherein the acyl group has a hydrocarbon group having 1 to 20 carbon atoms.   The resin composition according to claim 3, wherein the hydrocarbon group is a methyl group.   The resin composition according to claim 1, wherein the phenoxy resin (A) is a phenoxy resin containing a naphthalene skeleton in an amount of 10 to 60% based on the weight of the phenoxy resin (A).   The phenoxy resin (A) obtained by reacting a bifunctional epoxy resin and a bifunctional phenol compound in a combination in which at least one of the bifunctional epoxy resin and the bifunctional phenol compound contains a naphthalene skeleton The resin composition according to claim 1.   The resin composition according to claim 6, wherein the bifunctional epoxy resin is an epoxy resin containing a 3,3 ', 5,5'-tetramethylbiphenol skeleton, and the bifunctional phenol compound is a phenol compound containing a naphthalene skeleton.   The resin composition according to claim 1, wherein the phenoxy resin (A) is a phenoxy resin containing a bisphenol S skeleton. A phenoxy resin having a structure represented by the following general formula (1) and having a weight average molecular weight of 5,000 to 200,000.

(In the formula, A is a hydrogen atom or a group represented by the following general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a is 20 or more. It is an integer.

The phenoxy resin according to claim 9, wherein R ₁ is an acetyl group.   The phenoxy resin according to claim 9, comprising 10 to 60% by weight of the structure represented by the general formula (1). A phenoxy resin having a structure represented by the following general formula (3) and having a weight average molecular weight of 5,000 to 200,000 .

In the formulas, A is a group represented by hydrogen atom or the following general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and B is a hydrocarbon having 1 to 30 carbon atoms. Moreover, a1 is 20-800. ]

The phenoxy resin according to claim 12, wherein B in the general formula (3) has a structure represented by the following general formula (4).

[Wherein, R _{2 to} R ₉ may be the same or different and each represents a hydrogen atom or a methyl group . R ₁₀ is a direct bond, one or more structure selected from the group consisting of a hydrocarbon structure Contact and the following formula of 1 to 18 carbon atoms (5). ]

(In the formula, R _{11 to} R ₁₈ may be the same or different and each represents a hydrogen atom or a methyl group.) The phenoxy resin according to claim 12, comprising a structure represented by the following general formula (6).

[Wherein, A represents a hydrogen atom or a group represented by the general formula (2). R ₁ is an acyl group having a hydrocarbon group having 1 to 20 carbon atoms, and a2 is 20 to 800. ]   A coating composition comprising the resin composition according to claim 1.   An adhesive composition comprising the resin composition according to claim 1.   An adhesive film formed by forming a thin film of the resin composition according to claim 1 on a support base film.   A prepreg obtained by coating and / or impregnating a sheet-like reinforcing base material comprising fibers with the resin composition according to any one of claims 1 to 8.   A plated conductor layer is formed on a cured product obtained by curing the resin composition according to any one of claims 1 to 8, and the other surface is adhered and laminated to a patterned internal circuit board. Multi-layer printed wiring board.   A resin-coated copper foil obtained by applying the resin composition according to claim 1 to a copper foil.