JP6183918B2 - Polyhydroxy polyether resin, method for producing polyhydroxy polyether resin, resin composition containing polyhydroxy polyether resin, and cured product obtained therefrom - Google Patents

Description

The present invention is used as an anisotropic conductive adhesive film, an electrical laminate, a magnetic tape binder, an insulating varnish, an electric / electronic field such as a self-bonding enameled electric wire varnish, an adhesive, an insulating paint, a film, etc. A polyhydroxy polyether resin characterized by containing an indanyl group or α-methylbenzyl group having excellent water resistance, adhesion and dielectric properties as an essential component, a method for producing the polyhydroxy polyether resin, The present invention relates to a resin composition containing a resin, an insulating resin film, and an electronic circuit board.

Conventionally, polyhydroxypolyether resins are generally known as phenoxy resins and have excellent flexibility, impact resistance, insulation, adhesion, mechanical properties, etc. Used as a base resin for molding, a fluidity modifier added to epoxy resin varnishes, or an additive for improving the toughness of cured products. In the electrical and electronic fields, electrical machines such as magnetic tape binders and motors are used. Are used in a wide range of applications such as insulating varnishes, adhesives and films for circuit boards. In particular, printed wiring boards are becoming smaller, lighter, and more functional. Especially, for multilayer printed wiring boards, higher multilayers, higher density, thinner, lighter weight, higher reliability, and more. Molding processability is required. In response to this demand, a new multilayer printed wiring board manufacturing method such as a build-up method has been developed, and a high-performance resin suitable for these methods is required. As a copper foil with a resin for a build-up wiring board and a resin for an adhesive film, a polyhydroxy polyether resin has been studied because it is advantageous for film forming properties. As performance requirements for this polyhydroxypolyether resin, there has been a strong demand for lower dielectric constant and lower dielectric loss of the resin in accordance with recent demands for higher transmission speed of electrical signals. There are also demands for high heat resistance and low water absorption from the viewpoint of improving reliability. Conventionally studied polyhydroxy polyether resins include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, brominated epoxy resins, and the like. Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4 Describes a thermoplastic polyhydroxy polyether resin having a fluorene skeleton introduced therein, but these resins cannot sufficiently satisfy the above-mentioned requirements for high reliability and low dielectric constant.

Patent Document 1: JP-A-11-269264 Patent Document 2: JP-A-11-279260 Patent Document 3: JP-A-11-302373 Patent Document 4: JP-A-2003-252951

When a polyhydroxy polyether resin known so far is used for a resin composition for an electronic circuit board, the moldability, flexibility, impact resistance and adhesion can be improved. Sometimes , heat resistance, low water absorption, insulating properties and dielectric properties are deteriorated. The problems to be solved by the present invention are to solve various problems of conventional polyhydroxy polyether resins, heat resistance, low water absorption, electrical characteristics (particularly, low dielectric constant and low dielectric loss), molding An object of the present invention is to provide a polyhydroxypolyether resin and a resin composition for an electronic circuit board that are necessary for obtaining a resin composition for an electronic circuit board having excellent properties, flexibility, impact resistance, and adhesiveness.

The present invention for solving the above problems is selected from the following inventions.

(1) The polyhydroxy polyether resin represented by the following general formula (1) and having a weight average molecular weight of 10,000 to 200,000 has an indanyl group , an α-methylbenzyl group, or both substituents. A polyhydroxy polyether resin characterized by

Wherein A is a chemical structure represented by the following general formula (2) or the following general formula (3), and at least one of A has the indanyl group or α-methylbenzyl group as a substituent. (2) or a chemical structure represented by the general formula (3), B represents a hydrogen atom or a glycidyl group, n represents the number of repetitions, and represents an average value of 25 to 500.)

(In the formula, R is a group selected from the group consisting of an indanyl group or α-methylbenzyl group, a C 1-10 hydrocarbon group, a phenyl group or naphthyl group which may contain a hydrocarbon group, and a halogen element. Yes, they may be different or the same, and p represents an integer of 0 to 4.)

（式中、Ｒ_１及びＲ_２は、それぞれ独立にインダニル基又はα−メチルベンジル基、炭素数１〜１０炭化水素基、炭化水素基を含有していても良いフェニル基又はナフチル基、ハロゲン元素からなる群から選ばれる基であり、それぞれは異なっていても同一でも良く、ｐ及びｑは独立に０〜４の整数を示す。Ｘは単結合、炭素数１〜７の２価の炭化水素基、ベンジリデン基、α−メチルベンジリデン基、９Ｈ−フルオレン−９−イリデン基、−Ｏ−、−Ｓ−、−ＳＯ２−、又は、−ＣＯ−から選ばれる基であり、Ｘが芳香族骨格の場合は置換基として炭化水素基を含有していても良い。）

(Wherein R ₁ and R ₂ are each independently an indanyl group or α-methylbenzyl group, a C 1-10 hydrocarbon group, a phenyl group or naphthyl group optionally containing a hydrocarbon group, a halogen element Each of which may be different or the same, and p and q independently represent an integer of 0 to 4. X is a single bond and a divalent hydrocarbon having 1 to 7 carbon atoms. Group, benzylidene group, α-methylbenzylidene group, 9H-fluorene-9-ylidene group, —O—, —S—, —SO 2 —, or —CO—, and X is an aromatic skeleton In some cases, it may contain a hydrocarbon group as a substituent.)

(2) In the method for producing a polyhydroxy polyether resin as described in (1) above, wherein a dihydric phenol compound and epihalohydrin are reacted in the presence of an alkali, the indanyl group, α-methylbenzyl group, or both substituents as the dihydric phenol compound as essential components represented by the following general formula (5) having, year characterized by using epihalohydrin 0.985 to 1.015 mol of the dihydric phenol compound 1 mole (1) according to claim A method for producing a polyhydroxy polyether resin.

(Wherein R1 and R2 are each independently an indanyl group or α-methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group optionally containing a hydrocarbon group, or a halogen element) Each of which may be different or the same, but at least one of them represents an indanyl group or an α-methylbenzyl group, p and q independently represent an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8. X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an α-methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from —S—, —SO 2 —, or —CO—, and when X is an aromatic skeleton, it may contain a hydrocarbon group as a substituent.

(3) In the method for producing a polyhydroxy polyether resin as described in (1) above, wherein a bifunctional epoxy resin and a dihydric phenol compound are reacted in the presence of a catalyst, an indanyl group, an α-methylbenzyl group, or both bifunctional epoxy resins represented by the following general formula (6) having a substituent, or an indanyl group, alpha-methylbenzyl group, or a divalent represented by the following following general formula (5) with both of the substituents The method for producing a polyhydroxy polyether resin according to item (1), wherein at least one of the phenol compounds is used as an essential component.

（式中、Ｒ１及びＲ２は、それぞれ独立にインダニル基又はα−メチルベンジル基、炭素数１〜１０の炭化水素基、炭化水素基を含有していても良いフェニル基又はナフチル基、又はハロゲン元素から選ばれる基であり、それぞれは異なっていても同一でも良いが、少なくとも１つはインダニル基又はα−メチルベンジル基を示す。ｐ及びｑは独立に０〜４の整数を示し、ｐ＋ｑの合計は平均値で１〜８である。Ｘは単結合、炭素数１〜７の２価の炭化水素基、ベンジリデン基、α−メチルベンジリデン基、９Ｈ−フルオレン−９−イリデン基、−Ｏ−、−Ｓ−、−ＳＯ２−、又は、−ＣＯ−から選ばれる基であり、Ｘ中の芳香族骨格は置換基として炭化水素基を含有していても良い。Ｇはグリシジル基を示す。ｍは繰り返し数を示す。）

(Wherein R1 and R2 are each independently an indanyl group or α-methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group optionally containing a hydrocarbon group, or a halogen element) Each of which may be different or the same, but at least one of them represents an indanyl group or an α-methylbenzyl group, p and q independently represent an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8. X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an α-methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from -S-, -SO2-, or -CO-, and the aromatic skeleton in X may contain a hydrocarbon group as a substituent, G represents a glycidyl group, and m represents a glycidyl group. Indicates the number of repetitions.)

(4) An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the polyhydroxy polyether resin described in (1) above is an essential component.
(5) A resin composition for an electronic circuit board obtained by blending the polyhydroxy polyether resin described in the above (1).
(6) The adhesive film obtained from either the epoxy resin composition as described in said (4) term, or the resin composition for electronic circuit boards as described in said (5) term.

(7) Either an epoxy resin composition described in the above item (4) or a resin composition for electronic circuit boards described in the above item (5) is applied to a metal foil, and dried as necessary. Metal foil with resin.

(8) A glass cloth is impregnated with either the epoxy resin composition described in the above item (4) or the resin composition for an electronic circuit board described in the above item (5), and is obtained by drying as necessary. Prepreg.

(9) The epoxy resin composition according to (4), the resin composition for an electronic circuit board according to (5), the adhesive film according to (6), and the (7) A cured product obtained by curing either the metal foil with resin or the prepreg described in the above item (8).

The polyhydroxy polyether resin and the epoxy resin composition of the present invention are excellent in glass transition temperature, low dielectric constant (ε), low dielectric loss (tan δ), low water absorption, and particularly an electronic circuit requiring low dielectric constant characteristics. Exhibits excellent effects in substrate applications.

Hereinafter, the present invention will be described in detail.
The polyhydroxy polyether resin represented by the general formula (1) of the present invention has an indanyl group represented by the following general formula (4a) or an α-methylbenzyl group represented by the following general formula (4b) as a substituent. It is essential to have. These groups are those in which indene or styrene is substituted on the benzene ring of the dihydric phenol compound by Friedel-Crafts reaction. By having these substituents, water absorption resistance, heat resistance, and dielectric properties are improved. An indanyl group is preferable from the viewpoint of water absorption resistance and high heat resistance, and an α-methylbenzyl group is preferable from the viewpoint of low viscosity. Moreover, even if it has indanyl group or (alpha) -methylbenzyl group , the characteristics, such as adhesiveness which the polyhydroxy polyether resin without those substituents originally had, are not impaired. The effect tends to improve in proportion to the number of these substituents. In addition, when there are a plurality of substituents, the indanyl group or the α-methylbenzyl group may be the same or different.

Since the polyhydroxy polyether resin of the present invention is effective if there are substituents of these essential components, its content is not particularly specified, but is preferably in the range of 5 to 50% by mass, more preferably Is in the range of 8-40% by mass, more preferably in the range of 10-30% by mass.

The polyhydroxy polyether resin of the present invention has a weight average molecular weight (Mw) in the range of 10,000 to 200,000. Here, a weight average molecular weight means the polystyrene conversion weight average molecular weight by gel permeation chromatography. If Mw is less than 10,000, the thermoplasticity is lost and sufficient film performance cannot be obtained, and if it exceeds 200,000, the viscosity becomes extremely high and handling becomes difficult. From the viewpoint of both film performance and resin handling, the range of the weight average molecular weight is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and still more preferably 20 , 50,000 to 50,000.

The epoxy equivalent of the polyhydroxy polyether resin of the present invention is not particularly limited, but may be 5,000 g / eq or more. If it is less than 5,000 g / eq, the performance as a film is not sufficiently exhibited. If it is 5,000 g / eq or more, the film performance is improved, which is preferable.

The polyhydroxy polyether resin of the present invention may be substituted with an essential component by introducing the above-mentioned dihydric phenol compound, indanyl group , α-methylbenzyl having an indanyl group , an α-methylbenzyl group, or both. This is possible by using the above-mentioned bifunctional epoxy resin having both groups or both, or both.

As a method for producing the polyhydroxy polyether resin of the present invention, an epihalohydrin such as epichlorohydrin or epibromohydrin and a dihydric phenol compound having a substituent of indanyl group , α-methylbenzyl group, or both are contained as essential components. A one-step process for producing a dihydric phenol compound by reacting in the presence of an alkali, a dihydric phenol compound having an indanyl group , an α-methylbenzyl group, or both, an indanyl group , an α-methylbenzyl group, or There is a two-stage method in which a dihydric phenol compound and a bifunctional epoxy resin are generally reacted in the presence of a catalyst, which contains at least one of bifunctional epoxy resins having both substituents as essential components. The polyhydroxy polyether resin used in the present invention may be obtained by any production method.

The weight average molecular weight and epoxy equivalent of the polyhydroxy polyether resin of the present invention are the molar ratio of epihalohydrin and dihydric phenol compound in the one-stage method, and the molar ratio of bifunctional epoxy resin and dihydric phenol compound in the two-stage method. The thing of the target range can be manufactured by adjusting.

The divalent phenol compound having an indanyl group , an α-methylbenzyl group, or both substituents is preferably a divalent phenol compound having a biphenol skeleton or a bisphenol skeleton represented by the following general formula (5).

( Wherein R1 and R2 are each independently an indanyl group or α-methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group optionally containing a hydrocarbon group, or a halogen element) Each of which may be different or the same, but at least one of them represents an indanyl group or an α-methylbenzyl group, p and q independently represent an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8. X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an α-methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from —S—, —SO 2 —, or —CO—, and when X is an aromatic skeleton, it may contain a hydrocarbon group as a substituent.

In the dihydric phenol compound of the general formula (5), the number of indanyl groups or α-methylbenzyl groups is preferably in the range of 0.5 to 3.0, more preferably 0.5 to 3.0. It is the range of 1.5, More preferably, it is the range of 0.5-1.0. If it is smaller than this, the properties of the substituent will not improve water absorption resistance, heat resistance, and dielectric properties.

In order to introduce the substituent essential to the polyhydroxy polyether resin of the present invention into the dihydric phenol compound, the dihydric phenol compound is reacted with indene or styrene. The amount of indene or styrene used at that time substantially corresponds to the desired number of substituted moles (number of moles of substituents relative to 1 mole of the dihydric phenol compound), and the amount used may be determined accordingly. In addition, although reaction conditions in which any of the raw materials remain unreacted can be employed, the amount of indene or styrene used in 1 mol of the dihydric phenol compound is still in the range of 0.5 to 3.0 mol. It is preferable. When the reaction exceeds 3 mol, the effect of improving water absorption, heat resistance, dielectric properties, etc. is reduced despite the fact that the time required for the addition reaction is greatly increased. It is preferable to control to the following. Further, when any raw material remains unreacted, it is desirable to separate it, but it may remain as long as it is in a small amount. Further, when a large amount of indene or styrene is used, unreacted indene or styrene may remain, or a polymer of indene or styrene may be generated, which is not suitable as a raw material for the polyhydroxy polyether resin. In that case, it is necessary to separate and remove those impurities to achieve high purity. The purity of the dihydric phenol compound is preferably 96% by mass or more, and preferably 98% by mass or more.

A mixture of these may be used as indene or styrene to be reacted with the dihydric phenol compound, but those having styrene as the main component are preferable from the viewpoint of low viscosity, and those having indene as the main component from the viewpoint of heat resistance. Those are preferred.

The indene or styrene used for the reaction may contain an unsaturated bond-containing component such as α-methylstyrene, divinylbenzene, coumarone, benzothiophene, indole, or vinylnaphthalene as another reactive component. The indene and styrene contents in all reaction components are 60% by mass or more, preferably 80% by mass or more. If it is less than this, the effect of improving heat resistance and electrical characteristics is small. In addition, the compound which has a substituent derived from these is contained in the dihydric phenol compound obtained. The dihydric phenol compound used as a raw material for the polyhydroxy polyether resin of the present invention may contain a dihydric phenol compound having such a substituent. Similarly, the polyhydroxy polyether resin obtained by the method for producing a polyhydroxy polyether resin of the present invention may include a polyhydroxy polyether resin having such a substituent. Indene or styrene may contain non-reactive compounds such as toluene, dimethylbenzene, trimethylbenzene, indane, naphthalene, methylnaphthalene, dimethylnaphthalene, acenaphthene, and the like. From the viewpoint of improving properties such as heat resistance and electrical properties, it is better to remove these non-reactive compounds out of the system. Preferably, it is removed until it becomes 5 mass% or less of the whole, More preferably, it becomes 2 mass% or less. As a removal method, generally, a method such as vacuum distillation is applied.

For the reaction between the dihydric phenol compound and indene or styrene, a reaction method using a known Friedel-Crafts catalyst such as an acid catalyst can be employed. By this reaction, a divalent phenol compound having an indanyl group , an α-methylbenzyl group, or both substituents on the benzene ring of the divalent phenol compound is obtained. After completion of the reaction between the dihydric phenol compound and indene or styrene, the catalyst or unreacted components are removed as necessary to obtain a synthetic raw material for polyhydroxy polyether resin. However, it does not need to be removed even if it does not interfere with the synthesis of the polyhydroxy polyether resin, or is removed by a purification step such as washing and distillation at the time of synthesis or may be contained in the polyhydroxy polyether resin. Use of the reaction product after completion of the reaction between the dihydric phenol compound and indene or styrene as a raw material for synthesizing the polyhydroxy polyether resin is advantageous in that one purification step is required. A dihydric phenol compound can also be purified or isolated as a target product.

The divalent phenol compound used in the production of the one-stage method and the two-stage method of the polyhydroxy polyether resin of the present invention is a divalent phenol compound having a substituent of indanyl group , α-methylbenzyl group, or both. However, as long as the object of the present invention is not impaired, a compound having two hydroxyl groups bonded to an aromatic ring in other molecules may be used in combination. Examples of dihydric phenol compounds that may be used in combination include bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, bisphenol Z, bisphenol acetophenone, bisphenol fluorenone, biphenols, catechol, And monocyclic dihydric phenols such as resorcin and hydroquinone. These may be substituted with a substituent that does not have an adverse effect such as an alkyl group or an aryl group. These dihydric phenol compounds can be used in combination of a plurality of types.

In the case of the one-stage method among the methods for producing the polyhydroxy polyether resin of the present invention, the epihalohydrin is 0.985 to 1.015 mol, preferably 0.99 to 1.012 mol, more preferably, relative to 1 mol of the dihydric phenol compound. By reacting 0.995 to 1.01 mol in the presence of an alkali metal hydroxide in a non-reactive solvent, so that the epihalohydrin is consumed and the weight average molecular weight is 10,000 or more. A polyhydroxy polyether resin can be obtained. Examples of the non-reactive solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, ethanol, isopropyl alcohol, butyl alcohol, methyl cellosolve, ethyl cellosolve, and cyclohexanone, but are not particularly limited thereto. These solvents may be used alone or in combination of two or more. The reaction temperature is preferably 40 to 200 ° C, particularly preferably 60 to 170 ° C. The reaction pressure is usually atmospheric pressure. In addition, when it is necessary to remove the reaction heat, it is usually carried out by an evaporation / condensation / reflux method of the solvent used by the reaction heat, an indirect cooling method, or a combination thereof.

The bifunctional epoxy resin having substituents of indanyl group , α-methylbenzyl group, or both, which is the raw epoxy resin of the two-stage method in the method for producing the polyhydroxy polyether resin of the present invention, is preferably the above-mentioned It is a bifunctional epoxy resin represented by the following general formula (6) obtained by reacting a dihydric phenol compound represented by the general formula (5) with epihalohydrin.

(Wherein R1 and R2 are each independently an indanyl group or α-methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group optionally containing a hydrocarbon group, or a halogen element) Each of which may be different or the same, but at least one of them represents an indanyl group or an α-methylbenzyl group, p and q independently represent an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8. X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an α-methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from -S-, -SO2-, or -CO-, and the aromatic skeleton in X may contain a hydrocarbon group as a substituent, G represents a glycidyl group, and m represents a glycidyl group. Indicates the number of repetitions.)

In general formula (2), general formula (3), general formula (5), and general formula (6), R, R _{1, and} R ₂ are each independently an indanyl group, an α-methylbenzyl group, or a carbon number of 1 -10 hydrocarbon group, a phenyl group or naphthyl group which may contain a hydrocarbon group, or a halogen element. Among the substituents other than indanyl group or α-methylbenzyl group, as the hydrocarbon group having 1 to 10 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, Aralkyl groups having 7 to 10 carbon atoms are preferred, and the phenyl group or naphthyl group which may contain a hydrocarbon group includes phenyl groups having 6 to 12 carbon atoms or naphthyl groups having 10 to 16 carbon atoms. It is done. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n A linear or branched alkyl group having 1 to 10 carbon atoms such as a decyl group, a cyclic alkyl group having 3 to 10 carbon atoms such as a cyclohexyl group or a trimethylcyclohexyl group, a benzyl group, a phenethyl group, a 2-methylbenzyl group, A hydrocarbon group having 1 to 10 carbon atoms such as a 7 to 10 carbon aralkyl group such as a 3-methylbenzyl group, a 4-methylbenzyl group, a 2,6-dimethylbenzyl group, and a 3,5-dimethylbenzyl group; Preferred examples include phenyl or naphthyl substituents which may contain hydrocarbon groups such as phenyl, naphthyl, tolyl, trityl and xylyl groups. Group is a methyl group, an ethyl group, tert- butyl group, a cyclohexyl group, a phenyl group. These substituents may be one kind or plural kinds.

In the reaction of the dihydric phenol compound and the epihalohydrin to obtain the raw material epoxy resin of the two-stage method, 0.80 to 1.20 times equivalent to the hydroxyl group in the dihydric phenol compound, preferably 0.85 to 1 .05 equivalents of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are used. If it is less than this, the amount of remaining hydrolyzable chlorine increases, which is not preferable. The metal hydroxide is used in the form of an aqueous solution, alcohol solution or solid.

In the epoxidation reaction, an excessive amount of epihalohydrin is used with respect to the dihydric phenol compound. Usually, 1.5 to 15 times mole of epihalohydrin is used per mole of hydroxyl group in the dihydric phenol compound, but preferably in the range of 2 to 8 times mole. If the amount is more than this, the production efficiency is lowered, and if it is less than this, the amount of the high molecular weight polymer of the epoxy resin increases, and it is not suitable for the raw material of the polyhydroxy polyether resin.

The epoxidation reaction is usually performed at a temperature of 120 ° C. or lower. If the temperature is high during the reaction, the amount of so-called hardly hydrolyzable chlorine increases and it becomes difficult to achieve high purity. Preferably it is 100 ° C. or lower, more preferably 85 ° C. or lower.

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Among the methods for producing the polyhydroxy polyether resin of the present invention, the bifunctional epoxy resin used as the raw material for the two-stage method is preferably the bifunctional epoxy resin represented by the general formula (6). Any other compound may be used in combination as long as it is a compound having two epoxy groups in the molecule, so long as the purpose is not impaired. Examples of the bifunctional epoxy resin of the general formula (6) include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol acetophenone type epoxy resin, and bisphenol fluorenone type epoxy resin. And biphenol type epoxy resin. Among these epoxy resins, particularly preferred are bisphenol A type epoxy resin, bisphenol F type epoxy resin, diglycidyl ether of 4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4, 4'-biphenol diglycidyl ether, bisphenol acetophenone diglycidyl ether, and bisphenol fluorenone diglycidyl ether are preferred. If there is no indanyl group or α- methylbenzyl groups in the dihydric phenol compound, it is necessary at least one contains an indanyl group or α- methylbenzyl group bifunctional epoxy resin used. If a bifunctional epoxy resin having an indanyl group or an α-methylbenzyl group is used, other difunctional epoxy resins that may be used in combination are diglycidyl monocyclic dihydric phenol compounds such as catechol, resorcin, and hydroquinone. Examples include ether. These epoxy resins may be substituted with a substituent having no adverse effect such as an alkyl group or an aryl group. These epoxy resins can be used in combination of plural kinds.

In the case of the two-stage method among the methods for producing the polyhydroxy polyether resin of the present invention, a catalyst can be used as long as it is a compound having a catalytic ability to promote a reaction between an epoxy group and a phenolic hydroxyl group. Something like that. Examples thereof include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like. Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride. Alkali metal alkoxides such as sodium methoxide and sodium ethoxide, alkali metal phenoxides, sodium hydride, lithium hydride and the like, and alkali metal salts of organic acids such as sodium acetate and sodium stearate. Specific examples of the organic phosphorus compound include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, Trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, Triphenylethylphosphonium iodai , Triphenyl benzyl phosphonium chloride, triphenyl benzyl phosphonium bromide, and the like. 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. Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like. Specific examples of cyclic amines include 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5. These catalysts can be used in combination. Usually, the usage-amount of a catalyst is 0.001-1 mass% with respect to reaction solid content. When an alkali metal compound is used as a catalyst, an alkali metal component remains in the polyhydroxy polyether resin, and deteriorates the insulating properties of the printed wiring board using it, so that lithium, sodium in the polyhydroxy polyether resin, And the total content of potassium is preferably 5 ppm or less, more preferably 4 ppm or less, and even more preferably 3 ppm or less. If it is 5 ppm or more, the insulating properties deteriorate, which is not preferable. Also, when an organophosphorus compound is used as a catalyst, it remains as a catalyst residue in the polyhydroxypolyether resin and deteriorates the insulating properties of the printed wiring board. Therefore, the phosphorus content in the polyhydroxypolyether resin is preferable. Is 150 ppm or less, more preferably 140 ppm or less, and still more preferably 100 ppm or less. If it is 150 ppm or more, the insulating properties deteriorate, which is not preferable.

In the method for producing a polyhydroxy polyether resin in the present invention, a solvent may be used in the reaction step, and any solvent can be used as long as it dissolves the polyhydroxy polyether resin and does not adversely affect the reaction. But it ’s okay. Examples thereof include aromatic hydrocarbons, ketones, amide solvents, glycol ethers and the like. Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, and dioxane. Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like. Specific examples of glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -N-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate and the like. Two or more of these solvents can be used in combination. The amount of the solvent to be used can be appropriately selected according to the reaction conditions. For example, in the case of the two-stage production, it is preferable that the solid concentration is 35 to 95% by mass. Further, when a highly viscous product is produced during the reaction, the reaction can be continued by adding a solvent during the reaction. After completion of the reaction, the solvent can be removed by distillation or the like, if necessary, or further added.

The reaction temperature in the case of the two-stage method among the methods for producing the polyhydroxy polyether resin of the present invention is within a temperature range in which the catalyst used is not decomposed. The reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C. 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. In addition, when it is necessary to remove reaction heat, it is usually carried out by evaporation / condensation / reflux method of solvent used by reaction heat, indirect cooling method, or a combination thereof.

A halogen may be introduced into the polyoxypolyether resin of the present invention to impart flame retardancy. When flame retardancy is imparted by halogen, sufficient flame retardancy cannot be imparted if the halogen content is less than 5% by mass. Although flame retardancy can be imparted at any concentration at 5% by mass or more, no further improvement in flame retardancy is observed even at a concentration of 40% by mass or more, so the halogen content is 5-40% by mass. It is practical to control within this range. In the present invention, any halogen element may be used, but from the viewpoint of commercial production, it is preferable to use a commercially available bromine compound, chlorine compound or fluorine compound.

The resin composition for an electronic circuit board containing the polyhydroxy polyether resin of the present invention as an essential component includes, in addition to the polyhydroxy polyether resin, an epoxy resin, a curing agent, a curing accelerator, a solvent, an inorganic filler, and a fiber group. Various materials such as materials can be used in combination.

As an epoxy resin that can be used in combination, a normal epoxy resin having two or more epoxy groups in the molecule can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, phenols and aldehydes such as glyoxal, hydroxybenzaldehyde and crotonaldehyde Glycidyl ether type epoxy resins such as epoxy resins, aralkyl type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic epoxy resins, alicyclic rings obtained by reacting novolaks with epihalohydrins. Various epoxy resins such as epoxy resins, heterocyclic epoxy resins, phosphorus-containing epoxy resins, urethane-modified epoxy resins, and oxazolidone ring-containing epoxy resins. It is, but not limited thereto. These epoxy resins may be used alone or in combination of two or more. As specific examples, Epototo YD-128, Epototo YD-8125, Epototo YD-825GS (Nippon Steel & Sumikin Chemical Co., Ltd. bisphenol A type epoxy resin), Epototo YDF-170, Epototo YDF-8170, YDF-870GS (Nippon Steel & Sumitomo Metal) Chemical Co., Ltd. Bisphenol F type epoxy resin), YSLV-80XY (Nippon Steel & Sumikin Chemical Co., Ltd. Tetramethylbisphenol F type epoxy resin), Epototo YDC-1312 (Di-tert-butyl hydroquinone type epoxy resin), jERYX4000H (Mitsubishi Chemical) Biphenyl type epoxy resin), Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Nippon Steel & Sumikin Co., Ltd.), Epotot YDCN-701 (Nippon Steel & Sumikin Chemical Co., Ltd.) Renovolak type epoxy resin), Epototo ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), TX-0710 (Bisphenol S type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epicron EXA-1515 (Dainippon Chemical Industry) Bisphenol S type epoxy resin manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl phenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd., Epototo ZX-1355, Epototo ZX-1711 (Naphthalenediol type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Epototo ESN-155 (β-naphthol aralkyl epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epototo ESN-355, Epototo ESN-375 (Nippon Steel & Sumikin Chemical Co., Ltd., dinaphthol aralkyl) Type epoxy resin), Epototo ESN-475V, Epototo ESN-485 (Nippon Steel & Sumikin Chemical Co., Ltd. α-naphthol aralkyl type epoxy resin), EPPN-501H (Nippon Kayaku Co., Ltd. trisphenylmethane type epoxy resin), Sumiepoxy TMH-574 (Trisphenylmethane type epoxy resin manufactured by Sumitomo Chemical Co., Ltd.), YSLV-120TE (Bisthioether type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), Epototo ZX-1684 (Resorcinol type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Epoxy resins produced from polyphenolic phenolic compounds such as Epicron HP-7200H (DIC Corporation dicyclopentadiene type epoxy resin) and epihalohydrin, TX-0929, TX-0934, TX Epoxy resin produced from alcohol compounds such as 1032 (Nippon Steel Sumikin Chemical Co., Ltd. alkylene glycol type epoxy resin) and epihalohydrin, Celoxide 2021 (aliphatic cyclic epoxy resin produced by Daicel Chemical Industries, Ltd.), Epototo YH-434, Epoxy resin produced from an amine compound such as diaminodiphenylmethanetetraglycidylamine) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. and epihalohydrin, jER630 (aminophenol type epoxy resin manufactured by Mitsubishi Chemical Corporation), Epototo FX-289B, Epototo FX-305, Examples include phosphorus-containing epoxy resins obtained by reacting an epoxy resin such as TX-0932A (phosphorus-containing epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) with a modifier such as a phosphorus-containing phenol compound.

Examples of the curing agent that can be used in the resin composition of the present invention include various phenol compounds, acid anhydrides, amines, dicyandiamide, and the like. Specifically, as various phenol compounds, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol and the like Represented by tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. There are trivalent or higher phenol compounds. Furthermore, monohydric phenol compounds such as phenols and naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalenediol, etc. And polyhydric phenol compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and p-xylylene glycol. You may use what made indene or styrene react with these phenolic compounds for a hardening | curing agent. Acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, trimellitic anhydride, pyromellitic anhydride Acid, methyl nadic anhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3- Examples include dione, 1,2,3,4-butanetetracarboxylic dianhydride, hydrogenated pyromellitic acid anhydride, hydrogenated trimellitic acid anhydride, and the like. Examples of amines include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine. And aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine. These curing agents may be used alone or in combination of two or more. As addition amount of a hardening | curing agent, 10-100 mass parts is used as needed with respect to 100 mass parts of epoxy resins in the resin composition of this invention.

Furthermore, if necessary, a known curing accelerator can be used in the resin composition of the present invention. Specifically, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4 , 0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine and triphenylphosphine triphenylborane, metal compounds such as tin octylate, Lewis acids and the like. These curing accelerators may be used alone or in combination of two or more. As addition amount of a hardening accelerator, 0.02-5 mass parts is used as needed with respect to 100 mass parts of epoxy resins in the resin composition of this invention. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

Furthermore, you may add a solvent as needed. Specific examples of the solvent include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, methanol, ethanol, and the like. These solvents may be used alone or in combination of two or more.

Furthermore, a filler can be used as needed. Specifically, silica powder such as aluminum hydroxide, alumina, calcium carbonate, magnesium hydroxide, talc, calcined talc, clay, kaolin, boehmite, titanium oxide, glass powder, spherical or crushed fused silica, crystalline silica, silica Examples include inorganic fillers such as balloons. The reason for using a general inorganic filler is an improvement in impact resistance. Moreover, when metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, are used, it acts as a flame retardant adjuvant and can reduce the quantity of a flame retardant. In particular, if the blending amount is not 10 parts by mass or more with respect to 100 parts by mass of the epoxy resin in the resin composition of the present invention, the effect of impact resistance is small. However, if the blending amount exceeds 150 parts by mass, the adhesiveness, which is an item necessary for the use of laminates, is lowered. In addition, fiber base materials such as fiber fillers such as glass fiber, pulp fiber, synthetic fiber, ceramic fiber, fine particle rubber, thermoplastic elastomer, inorganic fiber cloth such as glass cloth, glass fiber nonwoven fabric, organic fiber nonwoven fabric, etc. In addition, an ultraviolet inhibitor, a plasticizer, and the like can be contained in the resin composition.

Furthermore, in the resin composition of the present invention, an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, or phenoxy resin may be appropriately blended, or pigment. In addition, additives such as a refractory agent, a thixotropic agent, a coupling agent, and a fluidity improver may be blended. Examples of the pigment include organic or inorganic extender pigments and scaly pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite. Furthermore, if necessary, the epoxy resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, Flame retardants such as antimony trioxide, low stress agents such as silicone oil, lubricants such as calcium stearate, and the like can be used.

These resin compositions can be used for new printed wiring boards such as conventional multilayer electronic circuit boards and build-up methods. In particular, use in the form of a resin-coated copper foil, an adhesive film, or the like used as a buildup method printed wiring board material is preferable. The build-up method is a build-up layer that is an insulating layer composed of a film (insulating layer) of 40 to 90 μm or a film with copper foil (copper foil: 9 to 18 μm) on an inner circuit board in which glass prepregs are laminated. In general, the circuit forming process includes a laminating press process, a drilling (laser or drill) process, and a desmear / plating process. And if it has the same performance as a conventional laminated board, both the mounting area and the mass are about 1/4, which is an excellent method for reducing the size and weight. In particular, the polyhydroxy polyether resin of the present invention is suitable for film formation and can be suitably used as a build-up insulating layer.

The method for producing the adhesive film according to the present invention is not particularly limited. For example, (i) the resin composition of the present invention is kneaded with an extruder and then extruded, and then formed into a sheet using a T die, a circular die, or the like. (B) a casting molding method in which the resin composition of the present invention is dissolved or dispersed in a solvent such as an organic solvent and then cast into a sheet, and (c) other conventionally known sheets. Examples include molding methods. Moreover, the film thickness of an adhesive film is although it does not specifically limit, For example, 10-300 micrometers, Preferably it is 25-200 micrometers, More preferably, it is 40-180 micrometers. When used in the build-up method, 40 to 90 μm is most preferable. If the film thickness is 10 μm or more, insulation can be obtained, and if it is 300 μm or less, the circuit distance between the electrodes does not become longer than necessary. In addition, although content of the solvent of an adhesive film is not specifically limited, It is preferable that it is 0.01-5 mass% with respect to the whole resin composition. If the content of the solvent in the film is 0.01% by mass or more with respect to the entire resin composition, adhesion and adhesiveness can be obtained when laminating to the circuit board, and if the content is 5% by mass or less. Flatness after heat curing is obtained.
EXAMPLES Hereinafter, although this invention is further demonstrated based on an Example, this invention is not limited to this.

In Examples, unless otherwise specified, “part” represents part by mass, and “%” represents mass%.
In the present invention, the following test methods and evaluation methods were used.

(1) Weight average molecular weight: It was measured as a standard polystyrene equivalent value by gel permeation chromatography. Specifically, the Tosoh Corporation HLC-8320 main body was used with a Tosoh Corporation column, TSK-gel GMHXL, TSK-gel GMHXL, and TSK-gel G2000HXL in series. The eluent was tetrahydrofuran and the flow rate was 1 ml / min. The temperature of the column chamber was 40 ° C. Detection was carried out using an RI detector and determined using a standard polystyrene calibration curve. As a measurement sample, 0.1 g of a sample was dissolved in 10 ml of THF.
(2) Epoxy equivalent: Measured according to JIS K 7236.
(3) Glass transition temperature: Extrapolated glass transition start temperature (Tig) of the DSC chart obtained in the second cycle of differential scanning calorimetry was defined as Tg [DSC]. Specifically, it was performed using DSC6200 manufactured by SII Nano Technology. A measurement sample was obtained by punching a resin film, laminating it, and packing it in an aluminum capsule. The measurement temperature range was from room temperature to 240 ° C. The temperature elevation rate was 10 ° C./min, and the measurement was performed for 2 cycles.

(4) Water absorption: As a water resistance index, measurement was performed using five test pieces obtained by cutting a resin film into 50 mm × 50 mm squares. The test piece was dried for 10 minutes at 100 ° C. in an air atmosphere using a hot air circulating oven, and the mass was measured immediately. The test piece was immersed in water at 25 ° C., and the water absorption rate was increased from the increment of mass after 48 hours. Asked.
(5) Dielectric constant ε (1 GHz) and dielectric loss tangent tan δ (1 GHz): cavity resonator perturbation method. Specifically, using a PNA network analyzer N5230A manufactured by Agilent Technologies, Inc. and a cavity resonator CP431 manufactured by Kanto Electronics Application Development Co., Ltd. under a measurement environment of room temperature 23 ° C. and humidity 50% RH, a width of 1.5 mm × Measurement was performed using a test piece of length 80 mm × film thickness 150 μm ± 50 μm.
(6) Copper foil peeling strength: measured in accordance with JIS C 6481.
(7) Solder heat resistance after PCT: As an index of water resistance, a test piece prepared according to JIS C 6481 was treated in an autoclave at 121 ° C. and 0.2 MPa for 1 hour, and then placed in a solder bath at 260 ° C. The case where no swelling or peeling occurred for 20 minutes or more was evaluated as ◯, the case where swelling or peeling occurred within 10 minutes was evaluated as X, and the others were evaluated as Δ.

Synthesis example 1
Into a four-necked glass separable flask equipped with a stirrer, a thermometer, a condenser, a nitrogen gas introducing device, and a dropping device, 684 parts of bisphenol A and 1800 parts of diglyme were charged and heated to 150 ° C. After melting, 19.5 parts of 48% sulfuric acid was added with stirring, and 348 parts of indene was added dropwise at 140 ° C. over about 3 hours. Further, the reaction was continued for 3 hours under total reflux. Thereafter, 33.4 parts of a 30% aqueous sodium carbonate solution was added for neutralization, and diglyme and water were removed under reduced pressure to obtain 1032 parts of an indene-added dihydric phenol compound in a yield of almost 100% (divalent). Phenol compound A). The obtained dihydric phenol compound had a hydroxyl equivalent of 172 g / eq. Met.

Synthesis example 2
The reaction was performed in the same manner as in Synthesis Example 1 except that 558 parts of 4,4′-biphenol was used instead of 684 parts of bisphenol A and 250 parts of styrene was used instead of 348 parts of indene, and 808 parts of a styrene-added dihydric phenol compound was added. Obtained (dihydric phenol compound B). The obtained dihydric phenol compound has a hydroxyl group equivalent of 135 g / eq. Met.

Synthesis example 3
Bisphenol F (4,4 'body (31%), 2,4' manufactured by Honshu Chemical Co., Ltd.) was added to a four-necked glass separable flask equipped with a stirrer, thermometer, condenser, nitrogen gas introducing device, and dropping device. 600 parts of the body (49%) and 2,2 'body (20%) were charged and the temperature was raised to 175 ° C. After melting, 0.44 part of p-toluenesulfonic acid was charged with stirring, and 624 parts of styrene was added dropwise at 175 ° C. over about 4 hours. Further, the reaction was continued for 3 hours under total reflux. Thereafter, the low boiling point component was removed under reduced pressure to obtain 1224 parts of a styrene-added dihydric phenol compound (dihydric phenol compound C). The obtained dihydric phenol compound had a hydroxyl group equivalent of 204 g / eq. Met.
In Synthesis Examples 1 to 3, the reaction rate of indene or styrene was almost 100%.

Synthesis example 4
Obtained in Synthesis Example 3 into a four-necked separable flask equipped with a stirrer, thermometer, continuous dripping device, and a device that cools and condenses the azeotropic vapor of epichlorohydrin and water under reduced pressure and returns only epichlorohydrin to the reaction system 2 450 parts of a monohydric phenol compound C, 918 parts of epichlorohydrin, and 138 parts of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 143.7 parts of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water and epichlorohydrin distilled under reflux were separated in the dropping tank in a separation tank, and epichlorohydrin was separated. Was returned to the reaction vessel, and water was removed from the system to react. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 516 parts of bifunctional epoxy resin with styrene (bifunctional epoxy resin A). The resulting bifunctional epoxy resin has an epoxy equivalent of 259 g / eq. Met.

Example 1
150 parts of dihydric phenol compound A, 82 parts of epichlorohydrin, 60 parts of toluene, 30 parts of n-butyl alcohol, 80 parts of 48.4% sodium hydroxide aqueous solution as a catalyst, stirrer, thermometer, condenser, nitrogen gas introduction device Was added to a four-necked glass separable flask, and while maintaining the reaction temperature at 60 ° C. to 70 ° C., 80 parts of toluene and 40 parts of n-butyl alcohol were added to the reaction for 3 hours during the reaction 2 hours. 65 parts of toluene and 35 parts of n-butyl alcohol were added to each and reacted for a total of 10 hours. Then, 5.5 parts of oxalic acid and 23.8 parts of pure water were added and neutralized to separate 117 parts of toluene. after adding n- butyl alcohol 56 parts, was washed twice with partial solution pure water was added to 78 parts of refluxing dehydration, epoxy equivalent 33,500g / eq, nonvolatile content 3 .0%, to obtain 680 parts of toluene · n-butyl alcohol mixed resin varnish polyhydroxy polyether resin having a weight average molecular weight 50,500. This mixed resin varnish was coated on a release film (PET) degreased with methyl ethyl ketone with a roller coater, dried in an air atmosphere at 150 ° C. for 2 hours using a hot air circulating oven, and then peeled off from the PET film. Thus, a resin film having a thickness of 60 μm was obtained. The properties of the resin thus obtained were analyzed for weight average molecular weight, epoxy equivalent, glass transition temperature, water absorption, dielectric constant ε (1 GHz), and dielectric loss tangent tan δ (1 GHz). The analysis results are as shown in Table 1.

Example 2
In a separable flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen blowing port, Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YD-128 (BPA type liquid epoxy resin, epoxy equivalent 187 g / eq, α diol concentration 7 meq / 100 g, Total chlorine concentration 0.16%) 175.3 parts, 124.7 parts of dihydric phenol compound B and 100 parts of cyclohexanone were charged, heated to 145 ° C., dissolved, and stirred for 1 hour. Thereafter, 0.12 part of 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., hereinafter abbreviated as 2E4MZ) was charged as a reaction catalyst, and the temperature was raised to 165 ° C. As the reaction proceeds, the viscosity of the reaction solution increases. However, stirring is continued to obtain a constant torque by adding cyclohexanone as appropriate, and after the addition of the catalyst, the polymerization reaction is carried out for 10 hours, and then the nonvolatile content is increased to 40% with methyl ethyl ketone. The mixture was diluted and mixed to obtain 990 parts of a polyhydroxy polyether resin methyl ethyl ketone / cyclohexanone mixed resin varnish having an epoxy equivalent of 19,000 g / eq, a nonvolatile content of 40.0% and a weight average molecular weight of 65,000. The solvent was removed from the mixed resin varnish for 1 hour using a vacuum oven at 170 ° C. and 0.2 kPa to obtain a polyhydroxy polyether resin. The obtained polyhydroxy polyether resin was diluted with tetrahydrofuran to a non-volatile content of 30%, coated on a PET film degreased with methyl ethyl ketone, and heated at 150 ° C. in an air atmosphere using a hot air circulating oven. After drying for a period of time, it was peeled off from the PET film to obtain a resin film having a thickness of 60 μm. The analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.

Example 3
Implemented except that 146.4 parts of Epototo YD-128, 153.6 parts of dihydric phenol compound C and 0.6 parts of triphenylphosphine (made by Hokuko Chemical Co., Ltd., trade name: TPP) were used as catalysts. A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.

Example 4
A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2 except that the raw material used was changed to 182 parts of bifunctional epoxy resin A, 118 parts of dihydric phenol compound A, and 0.12 part of 2E4MZ as a catalyst. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.

Example 5
ESF-300 (bisphenol fluorene type epoxy resin, epoxy equivalent 254 g / eq, α diol concentration 2 meq / 100 g, total chlorine concentration 0.12%) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. 206.5 parts, divalent phenol compound B A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2 except that 84.8 parts, resorcinol (special reagent grade) 8.7 parts, and TPP 0.6 parts as a catalyst were changed. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.

Example 6
101.7 parts of bifunctional epoxy resin A used by Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDC-1312 (hydroquinone type epoxy resin, epoxy equivalent 175 g / eq, α diol concentration 3 meq / 100 g, total chlorine concentration 0.11%) 66.1 parts, BPF (9,9′-bis (4-hydroxyphenyl) fluorene, hydroxyl equivalent = 175 g / eq) 132.2 parts by Osaka Gas Co., Ltd. A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.

Comparative Example 1
A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2, except that 197.5 parts of Epototo YD-128, 102.5 parts of bisphenol F, and 0.12 part of 2E4MZ were used as the catalyst. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.

Comparative Example 2
A mixed resin varnish and a resin film were obtained in the same procedure as in Example 2, except that the raw materials used were changed to 188.1 parts of Epototo YD-128, 111.9 parts of bisphenol A, and 0.6 parts of TPP. Moreover, the analysis similar to Example 1 was performed using the obtained resin film. The analysis results are as shown in Table 1.

From the results in Table 1, the polyhydroxy polyether resin containing an indanyl group or α-methylbenzyl group as a substituent in the resin has good heat resistance (high glass transition temperature) and good water resistance (water absorption). The electrical properties are good (low dielectric constant).

Examples 7-11, Comparative Examples 3-5
The polyhydroxy polyether resin obtained in Examples 1 to 3 and Comparative Examples 1 and 2, and an epoxy resin, an epoxy resin curing agent, a curing accelerator, and a solvent are mixed so as to satisfy the conditions described in Table 2, and nonvolatile An epoxy resin composition varnish having a content of 40% was obtained. At this time, the dicyandiamide used was a dicyandiamide solution prepared by dissolving in a mixed solvent comprising 4 parts of dicyandiamide, 15 parts of N, N-dimethylformamide and 15 parts of 2-methoxyethanol. Other than that, 50 parts of 2-methoxyethanol and 50 parts of methyl ethyl ketone were mixed and used with respect to 100 parts of the resin.

As other epoxy resins in the table, Epototo YD-128 and Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDCN-700-5 (orthocresol novolac type epoxy resin, epoxy equivalent 202 g / eq., Softening point 86 ° C.) As the epoxy resin curing agent, dicyandiamide and phenol novolac resin (BRG-557, Showa Denko KK, phenolic hydroxyl group equivalent 105 g / eq., Softening point 86 ° C.) and 2E4MZ were used as the curing accelerator.

  The epoxy resin composition varnish was impregnated into a glass cloth (WEA 116E 106S 136, 0.1 mm thickness, manufactured by Nittobo Co., Ltd.), and then the impregnated cloth was dried in a drying chamber at 150 ° C. for 8 minutes to obtain a B stage. A prepreg was obtained. Eight prepregs obtained by cutting this prepreg are sandwiched between two copper foils (3EC-III, 35 μm manufactured by Mitsui Mining & Smelting Co., Ltd.), and a vacuum press of 2 MPa under temperature conditions of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes To obtain a laminate. As physical property evaluation of the laminate thus obtained, glass transition temperature, copper foil peeling strength, and post-PCT solder heat resistance were analyzed. The analysis results are as shown in Table 2.

Table 2 shows the physical properties of the laminate produced using the resin composition containing the polyhydroxy polyether resin of the present invention shown in Table 2 and the properties of the laminate produced using the epoxy resin composition of the comparative example. As is clear from the comparison, the laminated board produced from the resin composition of the present invention is remarkably excellent in heat resistance (glass transition temperature), water resistance (solder heat resistance after PCT) and adhesion.

Claims (9)

The polyhydroxy polyether resin represented by the following general formula (1) and having a weight average molecular weight of 10,000 to 200,000 has an indanyl group, an α-methylbenzyl group, or both substituents. Polyhydroxy polyether resin.

(In the formula, A is a chemical structure represented by the following general formula (2) or the following general formula (3), and at least one of A is a general formula having an indanyl group or an α-methylbenzyl group as a substituent ( 2) or a chemical structure represented by the general formula (3), B represents a hydrogen atom or a glycidyl group, n represents the number of repetitions, and represents an average value of 25 to 500.

(In the formula, R is a group selected from the group consisting of an indanyl group or α-methylbenzyl group, a C 1-10 hydrocarbon group, a phenyl group or naphthyl group which may contain a hydrocarbon group, and a halogen element. Yes, they may be different or the same, and p represents an integer of 0 to 4.)

(In the formula, R1 and R2 each independently comprises an indanyl group or α-methylbenzyl group, a C 1-10 hydrocarbon group, a phenyl group or naphthyl group which may contain a hydrocarbon group, or a halogen element. Each of which may be different or the same, and p and q independently represent an integer of 0 to 4. X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, When benzylidene group, α-methylbenzylidene group, 9H-fluorene-9-ylidene group, —O—, —S—, —SO 2 —, or —CO— is selected, and X is an aromatic skeleton (It may contain a hydrocarbon group as a substituent.) The method of manufacturing a polyhydroxy polyether resin according divalent phenol compound with epihalohydrin in claim 1 is reacted in the presence of an alkali, indanyl group, alpha-methylbenzyl group, or the following general formula having both a substituent ( as an essential component a divalent phenol compound represented by 5), the method of manufacturing described polyhydroxy polyether resin to claim 1, 1 mole of dihydric phenol compound, characterized by using epihalohydrin 0.985 to 1.015 mol .

(Wherein R1 and R2 are each independently an indanyl group or α-methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group optionally containing a hydrocarbon group, or a halogen element) Each of which may be different or the same, but at least one of them represents an indanyl group or an α-methylbenzyl group, p and q independently represent an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8. X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an α-methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from —S—, —SO 2 —, or —CO—, and when X is an aromatic skeleton, it may contain a hydrocarbon group as a substituent. 2. The method for producing a polyhydroxy polyether resin according to claim 1, wherein the bifunctional epoxy resin and the dihydric phenol compound are reacted in the presence of a catalyst, having a substituent of indanyl group, [alpha] -methylbenzyl group, or both. bifunctional epoxy resins represented by the following general formula (6) or indanyl group, alpha-methylbenzyl group, or at least one of the dihydric phenol compound represented by the following following general formula (5) with both of the substituents The method for producing a polyhydroxy polyether resin according to claim 1, wherein one of them is used as an essential component.

(Wherein R1 and R2 are each independently an indanyl group or α-methylbenzyl group, a hydrocarbon group having 1 to 10 carbon atoms, a phenyl group or naphthyl group optionally containing a hydrocarbon group, or a halogen element) Each of which may be different or the same, but at least one of them represents an indanyl group or an α-methylbenzyl group, p and q independently represent an integer of 0 to 4, and the sum of p + q Is an average value of 1 to 8. X is a single bond, a divalent hydrocarbon group having 1 to 7 carbon atoms, a benzylidene group, an α-methylbenzylidene group, a 9H-fluorene-9-ylidene group, —O—, It is a group selected from -S-, -SO2-, or -CO-, and the aromatic skeleton in X may contain a hydrocarbon group as a substituent, G represents a glycidyl group, and m represents a glycidyl group. Indicates the number of repetitions.) The epoxy resin composition containing an epoxy resin and a hardening | curing agent, The polyhydroxy polyether resin of Claim 1 is made into an essential component, The epoxy resin composition characterized by the above-mentioned. The resin composition for electronic circuit boards formed by mix | blending the polyhydroxy polyether resin of Claim 1. The adhesive film obtained from either the epoxy resin composition of Claim 4, or the resin composition for electronic circuit boards of Claim 5. A metal foil with a resin obtained by applying any one of the epoxy resin composition according to claim 4 or the resin composition for electronic circuit boards according to claim 5 to a metal foil and drying it as necessary. A prepreg obtained by impregnating a glass cloth with either the epoxy resin composition according to claim 4 or the resin composition for an electronic circuit board according to claim 5 and drying as necessary. The epoxy resin composition according to claim 4, the resin composition for an electronic circuit board according to claim 5, the adhesive film according to claim 6, the metal foil with resin according to claim 7, or the claim 8 A cured product obtained by curing any of the prepregs described.