JP2022150653A - Phenoxy resin, resin composition thereof, and cured product thereof and method for producing the same - Google Patents

Abstract

To provide a phenoxy resin that is excellent in high thermal conductance, water resistance, and solvent solubility, a resin composition including the same, and a cured product thereof.SOLUTION: A phenoxy resin is represented by the formula (1) and has a weight average molecular weight of 10,000-200,000 (where, each X is a divalent group; 5-95 mol% of X are optionally substituted phenylene groups; each Z is a hydrogen atom or a glycidyl group; and each n is 10 or more and 500 or less on average).SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a phenoxy resin having high thermal conductivity, excellent solvent solubility and water resistance, and a method for producing the same. It also relates to a resin composition containing the phenoxy resin and a curable resin component and a cured product thereof.

Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, and electrical properties, so they are used in various fields such as adhesives, paints, civil engineering and construction materials, and electrical and electronic materials. ing. In particular, in the electrical and electronic fields, it is widely used in insulation casting, lamination materials, sealing materials, and the like.

Film formability is imparted by increasing the molecular weight by various methods. Such high molecular weight epoxy resins are called so-called phenoxy resins. In particular, bisphenol A type phenoxy resins are mainly used as base resins for paint varnishes, base resins for film molding, or added to epoxy resin varnishes to adjust fluidity, improve toughness when cured, and improve adhesiveness. Used for improvement purposes. Further, those having a phosphorus atom or a bromine atom in the skeleton are used as flame retardants blended in epoxy resin compositions and thermoplastic resins.

In recent years, laminate materials used in the electrical and electronic fields are becoming smaller, lighter, and more functional. Further, improvement in reliability and molding workability, etc. are required. Since the epoxy resin has the properties described above, it is suitably used in the field of multilayer circuit boards. However, in the electrical/electronics field and the power electronics field, where electronic circuits are becoming more dense and high-frequency, the amount of heat generated from electronic circuits is increasing. Gender is an issue. Conventionally, this heat dissipation has been covered by the thermal conductivity of the filler, but in order to achieve higher integration, it has become necessary to improve the thermal conductivity of the matrix epoxy resin itself.

Patent Document 1 describes a thermosetting resin composition using bisphenol A type epoxy resin, a phenol-based curing agent, and boron nitride particles as a thermally conductive filler as a heat dissipation/insulating material constituting electric/electronic equipment. It is
However, the bisphenol A type epoxy resin described in Patent Document 1 is insufficient in fluidity and thermal conductivity.

On the other hand, recently, several inventions have been disclosed that attempt to improve the thermal conductivity of the epoxy resin itself by introducing a mesogenic skeleton. For example, Patent Document 2 and Non-Patent Document 1 describe improvements in the thermal conductivity of epoxy resins by introducing various mesoghe skeletons, but considering cost, process, hydrolysis resistance and thermal stability Then it cannot be said to be practical.

Further, Patent Document 3 discloses an epoxy resin having good thermal conductivity using only a biphenyl skeleton. However, although it was film-forming and did not require modification such as adding a rubber component, its solvent solubility and heat resistance were insufficient.

JP 2015-193504 A Japanese Patent Application Laid-Open No. 2020-204029 JP 2013-151672 A

State-of-the-art technology of epoxy resin for electronic parts (CMC Publishing, 2006, Chapter 1 P24-31, Chapter 5 P114-121)

The present invention solves these problems, the resin itself has a high glass transition temperature, excellent solvent solubility, adhesiveness, and film-forming properties, and a balance of various properties such as thermal conductivity, heat resistance, and cured product properties. An object of the present invention is to provide a phenoxy resin capable of giving a cured product excellent in scalability, a resin composition using the same, a material for circuit boards, and a cured product thereof.

ここで、Ｘは２価の基であり、Ｘの５～９５モル％が下記式（２）で表されるフェニレン基であり、Ｚは独立に水素原子又はグリシジル基であり、ｎは繰り返し数の平均値であり、１０以上５００以下である。

ここで、Ｒ^１～Ｒ^４はそれぞれ独立に、水素原子、炭素数１～８のアルキル基、又はフェニル基のいずれかである。 That is, the present invention is a phenoxy resin characterized by being represented by the following formula (1) and having a weight average molecular weight of 10,000 to 200,000.

Here, X is a divalent group, 5 to 95 mol% of X is a phenylene group represented by the following formula (2), Z is independently a hydrogen atom or a glycidyl group, n is the repeating number is the average value of 10 or more and 500 or less.

Here, R ¹ to R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

ここで、Ｙはそれぞれ独立に、芳香族基、縮合芳香族基、脂環基、又は脂環式複素環基であり、Ｒ^５は、直接結合、炭素数１～２０の炭化水素基、又は－ＣＯ－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ＝Ｃ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＣＨ＝Ｎ－、－ＣＨ＝Ｎ－Ｎ＝ＣＨ－、－Ｎ＝Ｎ－、－Ｎ（Ｏ）＝Ｎ－、及び－Ｃ（ＣＦ_３）_２－からなる群から選ばれる２価の結合基である。
X above is preferably a phenylene group represented by the above formula (2) and a divalent group represented by the following formula (3).

Here, each Y is independently an aromatic group, a condensed aromatic group, an alicyclic group, or an alicyclic heterocyclic group, and R ⁵ is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or -CO-, -O-, -S-, -SO ₂ -, -C=C-, -C≡C-, -CO-O-, -CO-NH-, -CH=N-, -CH= It is a divalent linking group selected from the group consisting of NN=CH-, -N=N-, -N(O)=N- and -C(CF ₃ ) ₂ -.

ここで、Ｒ^６、Ｒ^７はそれぞれ独立に、水素原子、ｔ－ブチル基、又はｔ－オクチル基のいずれかである。

ここで、Ｒ^８～Ｒ^１５はそれぞれ独立に、水素原子、炭素数１～８のアルキル基、又はフェニル基のいずれかである。 X above is preferably a phenylene group represented by the following formula (4) and a biphenylene group represented by the following formula (5).

Here, R ⁶ and R ⁷ are each independently a hydrogen atom, a t-butyl group, or a t-octyl group.

Here, each of R ⁸ to R ¹⁵ is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

式（６）において、ｔ－Ｂｕはｔ－ブチル基である。 X preferably has both a phenylene group represented by the following formula (6) and/or formula (7) and a biphenylene group represented by the following formula (8) and/or formula (9).

In formula (6), t-Bu is a t-butyl group.

ここで、Ａ及びＢはいずれも２価の基であり、ＡとＢを合わせた５～９５モル％が下記式（２）で表されるフェニレン基である。Ｇはグリシジル基であり、ｍは繰り返し数の平均値であり、０以上６以下である。

ここで、Ｒ^１～Ｒ^４はそれぞれ独立に、水素原子、炭素数１～８のアルキル基、又はフェニル基のいずれかである。 Further, the present invention is obtained by reacting a bifunctional epoxy resin represented by the following formula (10) with a bifunctional phenol compound represented by the following formula (11), and has a weight average molecular weight of 10,000 to 200. ,000.

Here, both A and B are divalent groups, and 5 to 95 mol % of the total of A and B is a phenylene group represented by the following formula (2). G is a glycidyl group, m is the average number of repetitions, and is 0 or more and 6 or less.

Here, R ¹ to R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

ここで、Ｙはそれぞれ独立に、芳香族基、縮合芳香族基、脂環基、又は脂環式複素環基であり、Ｒ^５は、直接結合、炭素数１～２０の炭化水素基、又は－ＣＯ－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ＝Ｃ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＣＨ＝Ｎ－、－ＣＨ＝Ｎ－Ｎ＝ＣＨ－、－Ｎ＝Ｎ－、－Ｎ（Ｏ）＝Ｎ－、及び－Ｃ（ＣＦ_３）_２－からなる群から選ばれる２価の結合基である。 A and/or B preferably contain a phenylene group represented by the above formula (2) and a divalent group represented by the following formula (3).

Here, each Y is independently an aromatic group, a condensed aromatic group, an alicyclic group, or an alicyclic heterocyclic group, and R ⁵ is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or -CO-, -O-, -S-, -SO ₂ -, -C=C-, -C≡C-, -CO-O-, -CO-NH-, -CH=N-, -CH= It is a divalent linking group selected from the group consisting of NN=CH-, -N=N-, -N(O)=N- and -C(CF ₃ ) ₂ -.

The present invention also provides a resin composition containing 0.1 to 100 parts by mass of a curing agent as a solid content with respect to 100 parts by mass of the solid content of the phenoxy resin.

The present invention also provides a resin composition comprising the above phenoxy resin, an epoxy resin and a curing agent, wherein the mass ratio of the solid content of the phenoxy resin to the epoxy resin is 99/1 to 1/99, and the phenoxy resin and It is preferable to include 0.1 to 100 parts by mass of the curing agent as a solid content with respect to a total of 100 parts by mass of the solid content of the epoxy resin.

The above curing agents include acrylic acid ester resins, melanin resins, urea resins, phenol resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, cationic polymerization initiators, organic phosphines, polyisocyanate compounds, block It is preferably at least one selected from the group consisting of isocyanate compounds and active ester curing agents.

The resin composition preferably further contains an inorganic filler.

The present invention also provides a cured product obtained from the above resin composition, a circuit board material obtained from the above resin composition, and a laminate for electric/electronic circuits.

The present invention also provides a method for producing the above phenoxy resin, wherein a bifunctional epoxy resin containing a bifunctional epoxy resin represented by the above formula (10) and a bifunctional phenol compound represented by the above formula (11) are combined. A method for producing a phenoxy resin, characterized by reacting with a bifunctional phenol compound contained in the presence of a catalyst.

ここで、Ｒ^１～Ｒ^４はそれぞれ独立に、水素原子、炭素数１～８のアルキル基、又はフェニル基のいずれかであり、Ｙはそれぞれ独立に、芳香族基、縮合芳香族基、脂環基、又は脂環式複素環基であり、Ｒ^５は、直接結合、炭素数１～２０の炭化水素基、又は－ＣＯ－、－Ｏ－、－Ｓ－、－ＳＯ_２－、－Ｃ＝Ｃ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＣＨ＝Ｎ－、－ＣＨ＝Ｎ－Ｎ＝ＣＨ－、－Ｎ＝Ｎ－、－Ｎ（Ｏ）＝Ｎ－、及び－Ｃ（ＣＦ_３）_２－からなる群から選ばれる２価の結合基である。 Further, the present invention is characterized by reacting a bifunctional phenol compound represented by the following formula (12) and/or formula (13) with epihalohydrin in the presence of an alkali. It is a method for producing a phenoxy resin.

Here, R ¹ to R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and each Y is independently an aromatic group, a condensed aromatic group, an alicyclic a cyclic group or an alicyclic heterocyclic group, wherein R ⁵ is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or —CO—, —O—, —S—, —SO ₂ —, —C =C-, -C≡C-, -CO-O-, -CO-NH-, -CH=N-, -CH=N-N=CH-, -N=N-, -N(O)= It is a divalent linking group selected from the group consisting of N- and -C(CF ₃ ) ₂ -.

The phenoxy resin of the present invention is characterized in that the resin itself has a high glass transition temperature and is excellent in solvent solubility, adhesiveness, and film-forming properties. Moreover, the resin composition containing the phenoxy resin of the invention gives a thermally conductive and heat-resistant cured product. Since the resin composition gives a cured product having well-balanced electrical properties and adhesive properties, it can be advantageously used not only in the electric/electronic field but also in the pressure sensitive adhesive/adhesive field. Especially for laminates for printed wiring boards, build-up insulating layers, adhesives for flexible printed wiring boards and metal core laminates, resist inks, liquid semiconductor sealing materials, underfill materials, die bonding materials, or electrical and electronic applications. It is useful in applications as an adhesion improver and a flexibility imparting agent.

1 is a GPC chart of the phenoxy resin obtained in Example 1. FIG. 1 is an IR chart of the phenoxy resin obtained in Example 1. FIG.

ここで、Ｘは２価の基であり、Ｘの５～９５モル％が下記式（２）で表されるフェニレン基である。

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.
The phenoxy resin of the present invention is represented by the following formula (1).

Here, X is a divalent group, and 5 to 95 mol % of X is a phenylene group represented by the following formula (2).

The phenoxy resin of the present invention has a weight average molecular weight (Mw) of 10,000 to 200,000, preferably 20,000 to 150,000, more preferably 25,000 to 100, as measured by gel permeation chromatography (GPC). ,000 is more preferred, and 30,000 to 80,000 is even more preferred. If the Mw is low, the film formability and elongation are inferior, and if the Mw is too high, the handleability of the resin is remarkably deteriorated. The GPC measurement method follows the conditions described in Examples.

Unless otherwise specified, the phenoxy resin of the present invention includes a high-molecular-weight epoxy resin having epoxy groups (glycidyl groups) at both ends, a high-molecular-weight phenol resin having phenolic hydroxyl groups at both ends, and a terminal epoxy group and a terminal phenolic A general term for high-molecular-weight resins in which hydroxyl groups coexist. Generally, the epoxy equivalent weight (g/eq.) of phenoxy resins does not need to be specified because reaction with epoxy groups is not taken into consideration, but 4,000 or more is sufficient. If it is less than 4,000, the film formability and elongation are inferior, which is not preferable.
Similarly, considering that both ends are phenolic hydroxyl groups, the phenolic hydroxyl group equivalent (g/eq.) should be 4,000 or more. If it is less than 4,000, the film formability and elongation are inferior, which is not preferable. That is, the phenoxy resin of the present invention preferably has an epoxy equivalent and a phenolic hydroxyl group equivalent of 4,000 or more.

In the above formula (1), X is a divalent group, 5 to 95 mol % of which is a phenylene group represented by the above formula (2). The phenylene group represented by formula (2) is preferably 25 to 75 mol %, more preferably 30 to 70 mol %, still more preferably 40 to 60 mol %, in all X. Solvent solubility and high thermal conductivity can be expressed by having a phenylene group represented by Formula (2).
Each Y is independently a hydrogen atom or a glycidyl group.
n is the number of repetitions, and its average value is 10 to 500, preferably 25 to 400, more preferably 50 to 350, and even more preferably 70 to 300. n is related to Mw above.

The ratio of phenylene groups in X can be controlled by the ratio of raw materials, which will be described later in the section on the method for producing a phenoxy resin. Therefore, in the phenoxy resin of the present invention, when a plurality of types of bifunctional phenol compounds are used as raw materials in the phenoxy resin produced by the one-step method described later, the phenylene group-containing bifunctional phenol compound in the raw materials is regarded as the ratio of the phenylene group of X as it is. Similarly, in the case of the phenoxy resin produced by the two-step method described below, the molar ratio of the phenylene group-containing compound contained in each of the bifunctional epoxy resin and the bifunctional phenol compound used as raw materials is the phenylene group of X as it is. shall be regarded as the ratio of
As used herein, a bifunctional epoxy resin is an epoxy resin having substantially two epoxy groups, and a bifunctional phenol compound is a hydroxy compound having substantially two phenolic hydroxyl groups. That is.

In formula (2) above, R ¹ to R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group. The number of substituents other than hydrogen atoms is preferably 1 to 2, more preferably 2.

The bonding position of the phenylene group may be any of the para-position, the meta-position and the ortho-position, preferably the para-position and the meta-position, and more preferably the para-position.

The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- hexyl group, n-heptyl group, n-octyl group, isopropyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, t-octyl group, isohexyl group, cyclopentyl group, cyclohexyl group , cycloheptyl group, methylcyclohexyl group, cyclooctyl group, dimethylcyclohexyl group, ethylcyclohexyl group and the like.

Preferred R ¹ to R ⁴ are methyl group, ethyl group, isopropyl group, t-butyl group, t-octyl group, cyclohexyl group or phenyl group, and methyl group, ethyl group, t-butyl group and t-octyl group. , or a phenyl group is more preferred.

Examples of the phenylene group represented by the formula (2) include groups represented by the following formulas (2a) to (2h) in addition to the groups represented by the above formula (6) or (7). but not limited to these. Among these groups, groups represented by formula (6) or formula (7) are preferred.

ここで、Ｍｅはメチル基であり、ｔ－Ｂｕはｔ－ブチル基であり、Ｐｈはフェニル基である。

where Me is a methyl group, t-Bu is a t-butyl group and Ph is a phenyl group.

X essentially has 5 to 95 mol% of a phenylene group (X ¹ ) represented by the above formula (2), a divalent group (X ² ) represented by the following formula (3), and naphthylene Other groups (X ³ ) such as groups may be included.

X preferably contains 5 to 50 mol% of a divalent group (X ² ) represented by the above formula (3) together with the essential phenylene group (X ¹ ) represented by the above (2). .
Other groups (X ³ ) such as naphthylene groups are preferably less than 10 mol %.

In formula (3), each Y is independently an aromatic ring group, a condensed aromatic ring group, an alicyclic group, or an alicyclic heterocyclic group, preferably an aromatic ring group, and these aromatic ring groups is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or a carbon It may have an aralkyloxy group of numbers 7 to 12 as a substituent.

The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl and n- hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, isopropyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, isohexyl group, Cyclopentyl group, cyclohexyl group, cycloheptyl group, methylcyclohexyl group, cyclooctyl group, dimethylcyclohexyl group, ethylcyclohexyl group, trimethylcyclohexyl group, cyclodecyl group and the like.

The alkoxy group having 1 to 10 carbon atoms may be linear, branched or cyclic, and examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n -hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, isopropoxy group, sec-butoxy group, t-butoxy group, isopentyloxy group, neopentyloxy group , t-pentyloxy group, isohexyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, methylcyclohexyloxy group, cyclooctyloxy group, dimethylcyclohexyloxy group, ethylcyclohexyloxy group, trimethylcyclohexyloxy group, A cyclodecyloxy group and the like can be mentioned.

Examples of the aryl group or aryloxy group having 6 to 11 carbon atoms include phenyl group, tolyl group, ethylphenyl group, xylyl group, propylphenyl group, mesityl group, naphthyl group, methylnaphthyl group, phenoxy group and tolyloxy group. , ethylphenoxy group, xylyloxy group, propylphenoxy group, mesityloxy group, naphthyloxy group, methylnaphthyloxy group and the like.

Examples of the aralkyl group or aralkyloxy group having 7 to 12 carbon atoms include benzyl group, methylbenzyl group, dimethylbenzyl group, trimethylbenzyl group, phenethyl group, 1-phenylethyl group, 2-phenylisopropyl group and naphthylmethyl. group, benzyloxy group, methylbenzyloxy group, dimethylbenzyloxy group, trimethylbenzyloxy group, phenethyloxy group, 1-phenylethyloxy group, 2-phenylisopropyloxy group, naphthylmethyloxy group and the like.

Y is preferably a phenylene group, a naphthylene group, or an aromatic ring group in which these are substituted with a methyl group or a 1-phenylethyl group.

R ⁵ above is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or —CO—, —O—, —S—, —SO ₂ —, —C═C—, —C≡C—, —CO -O-, -CO-NH-, -CH=N-, -CH=N-N=CH-, -N=N-, -N(O)=N-, and -C(CF ₃ ) ₂ - A divalent linking group selected from the group consisting of

Hydrocarbon groups having 1 to 20 carbon atoms include -CH ₂ -, -CH(CH ₃ )-, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, cyclohexylene group, trimethylcyclohexylene group, cyclododecylene group, cyclopentylidene group, methylcyclopentylidene group, trimethylcyclopentylidene group, cyclooctylidene group, cyclododecylidene group, bicyclo[4.4.0]decylidene group, bicyclohexanediyl group, fluorene group, phenylene group, xylylene group, phenylmethylene group, diphenylmethylene group, norbornylene group, adamantylene group, tetrahydrodicyclopentadienylene group, tetrahydrotricyclopentadienylene group, norbornane structure, tetrahydrodicyclopentadiene structure, tetrahydrotricyclo A divalent group having a pentadiene structure or the like is included.

Preferred R ⁵ includes direct bond, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CO-, -O-, -S-, -SO ₂ -, cyclohexylene group, trimethylcyclohexylene group, cyclooctylidene group, cyclododecylidene group, bicyclohexanediyl group, fluorene group, phenylmethylene group, and a divalent group having a tetrahydrodicyclopentadiene structure, a direct bond, —CH _2- , -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, a trimethylcyclohexylene group, a fluorene group, a phenylmethylene group, and a divalent group having a tetrahydrodicyclopentadiene structure are more preferred.

ここで、Ｒ^６、Ｒ^７はそれぞれ独立に、水素原子、ｔ－ブチル基、又はｔ－オクチル基のいずれかである。

ここで、Ｒ^８～Ｒ^１５はそれぞれ独立に、水素原子、炭素数１～８のアルキル基、又はフェニル基のいずれかである。

式（６）において、ｔ－Ｂｕはｔ－ブチル基である。 In formula (1), as X, it is preferable to simultaneously have a phenylene group (X ¹ ) represented by the following formula (4) and a biphenyl group (X ² ) represented by the following formula (5). (X ¹ ) is more preferably a group represented by the following formula (6) or (7), and the biphenyl group (X ² ) is more preferably a group represented by the following formula (8) or (9).

Here, R ⁶ and R ⁷ are each independently a hydrogen atom, a t-butyl group, or a t-octyl group.

Here, each of R ⁸ to R ¹⁵ is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.

In formula (6), t-Bu is a t-butyl group.

The method for producing the phenoxy resin of the present invention includes, but is not limited to, the following one-step method and two-step method. The phenoxy resin of the present invention may be obtained by any production method, but it is generally easier to obtain a phenoxy resin by a two-step method than by a one-step method, so it is preferable to use a two-step method.

ここで、Ｙ、Ｒ^１～Ｒ^５の意味は、上述した式（２）、式（３）と同義である。 In the one-step method, an epihalohydrin such as epichlorohydrin or epibromhydrin and a bifunctional phenol compound having a phenylene group represented by the following formula (12) are essential, preferably a bifunctional phenol represented by the following formula (13). A mixture containing the compound is reacted in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide.

Here, the meanings of Y and R ¹ to R ⁵ are the same as in formulas (2) and (3) above.

ここで、Ａ及びＢはいずれも２価の基であり、上記式（２）で表されるフェニレン基を少なくとも１つ含む。Ｇはグリジル基である。ｍは繰り返し数で、その平均値は０～６であり、０～３が好ましく、０～１がより好ましい。 In the two-step method, a bifunctional epoxy resin represented by the following formula (10) and a bifunctional phenol compound represented by the following formula (11) are generally reacted in the presence of a catalyst. One or both of the bifunctional epoxy resin and the bifunctional phenol compound have a phenylene group represented by the above formula (2).

Here, both A and B are divalent groups and contain at least one phenylene group represented by the above formula (2). G is a glycyl group. m is the number of repetitions, and its average value is 0 to 6, preferably 0 to 3, more preferably 0 to 1.

The weight-average molecular weight and epoxy equivalent of the phenoxy resin can be achieved by adjusting the charged molar ratio of epihalohydrin and the bifunctional phenol compound in the one-step method, and by adjusting the charged molar ratio of the bifunctional epoxy resin and the bifunctional phenol compound in the two-step method. A range of products can be manufactured.

As the bifunctional phenol compound used in the production of the one-step method and the two-step method, a bifunctional phenol compound having a phenylene group represented by the above formula (12) is essential, and other bifunctional phenol compounds are used in combination. do. Bifunctional phenol compounds that may be used in combination include, for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol B, bisphenol E, bisphenol C, and bisphenolacetophenone, biphenols, catechol, resorcin, hydroquinone, and the like. monocyclic bifunctional phenols, dihydroxynaphthalenes, and the like. In addition, these bifunctional phenol compounds may be substituted with substituents having no adverse effects, such as alkyl groups and aryl groups. A plurality of these bifunctional phenol compounds may be used in combination.
Among these, the bifunctional phenol compound represented by the above formula (13) that gives the above formula (3) is preferred. Here, the bifunctional phenol compound has a broad meaning and is substantially synonymous with a bifunctional hydroxy compound having two phenolic hydroxyl groups.

First, the one-stage method will be described.
In the case of the one-step method, 0.985 to 1.015 mol, preferably 0.99 to 1.012 mol, more preferably 0.995 to 1.01 mol of epihalohydrin per 1 mol of the bifunctional phenol compound, A phenoxy resin can be obtained by reacting in the presence of an alkali metal hydroxide in a non-reactive solvent, consuming epihalohydrin, and subjecting the condensation reaction to a weight average molecular weight of 10,000 or more. After completion of the reaction, it is necessary to remove by-product salts by filtration or washing with water.

The ratio of the bifunctional phenol compound having a phenylene group represented by formula (12), which is an essential component used as a raw material, is 5 to 95 mol% in the raw material bifunctional phenol compound, and 25 to 75 mol%. Preferably, 30 to 70 mol % is more preferable, and 40 to 60 mol % is even more preferable.

This reaction can be carried out under normal pressure or under reduced pressure. The reaction temperature is usually preferably from 20 to 200°C, more preferably from 30 to 170°C, even more preferably from 40 to 150°C, particularly preferably from 50 to 100°C, when the reaction is carried out under normal pressure. In the case of the reaction under reduced pressure, the temperature is preferably 20 to 100°C, more preferably 30 to 90°C, even more preferably 35 to 80°C. If the reaction temperature is within this range, side reactions are less likely to occur and the reaction is likely to proceed. The reaction pressure is usually normal pressure. When the heat of reaction needs to be removed, it is usually carried out by evaporation/condensation/reflux of the solvent used, indirect cooling, or a combination thereof.

Examples of non-reactive solvents include aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; ethers such as dibutyl ether, dioxane and tetrahydrofuran; , isopropyl alcohol and butyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, and glycol ethers such as ethylene glycol dimethyl ether, but are not particularly limited to these solvents. may be used alone or in combination of two or more.

A catalyst can also be used. Usable catalysts include, for example, quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide; tertiary amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; Examples include imidazoles such as 2-ethyl-4-methylimidazole and 2-phenylimidazole, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine. These catalysts may be used alone or in combination of two or more.

Next, the two-step method will be explained.
The phenoxy resin of the present invention is obtained by reacting a bifunctional epoxy resin and a bifunctional phenol compound. At least one of the bifunctional epoxy resin and the bifunctional phenol compound necessarily has a phenylene group represented by the formula (2). The ratio of the bifunctional epoxy resin having a phenylene group and the bifunctional phenol compound is 5 to 95 mol%, 25 to 75 mol% with respect to the total number of moles of the bifunctional epoxy resin and the bifunctional phenol compound. mol % is preferred, 30 to 70 mol % is more preferred, and 40 to 60 mol % is even more preferred.

The bifunctional epoxy resin to be the raw material epoxy resin for the two-step method is not particularly limited as long as it is a bifunctional epoxy resin. Preferred is a bifunctional epoxy resin represented by the above formula (10) obtained by reacting a bifunctional phenol compound having a phenylene group represented by the above formula (2) with epihalohydrin.

For the reaction of the bifunctional phenol compound and epihalohydrin for obtaining the raw material epoxy resin of the two-step method, 0.80 to 1.20 mol, preferably 0.85 to 0.85 times the functional group in the bifunctional phenol compound. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are used in an amount of 1.05 times the molar amount. If it is less than this, the amount of residual hydrolyzable chlorine will increase, which is not preferable. As metal hydroxides, they are used in the form of aqueous solutions, alcoholic solutions or solids.

In the epoxidation reaction, an excess amount of epihalohydrin is used with respect to the bifunctional phenol compound. Generally, epihalohydrin is used in an amount of 1.5 to 15 times mol, preferably 2 to 10 times mol, more preferably 5 to 8 times mol, per 1 mol of the functional group in the bifunctional phenol compound. If it is more than this, the production efficiency will be lowered, and if it is less than this, the production amount of high molecular weight epoxy resin will increase and it will not be suitable as a raw material for phenoxy resin.

The epoxidation reaction is usually carried out at a temperature of 120°C or less. If the temperature is high during the reaction, the amount of so-called hardly hydrolyzable chlorine increases, making it difficult to achieve high purification. The temperature is preferably 100° C. or lower, more preferably 85° C. or lower.

The bifunctional epoxy resin represented by the formula (10) is preferable as the bifunctional epoxy resin used as the raw material of the two-step method, but other bifunctional epoxy resins may be used in combination as long as the object of the present invention is not impaired. Examples of bifunctional epoxy resins that can be used in combination 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, diphenyl sulfide type epoxy resin, and diphenyl ether type epoxy resin. monocyclic bifunctional phenol diglycidyl ethers such as resins, biphenol-type epoxy resins, hydroquinone-type epoxy resins, dihydroxynaphthalene-type epoxy resins, diphenyldicyclopentadiene-type epoxy resins, alkylene glycol-type epoxy resins, aliphatic cyclic epoxy resins, and the like. be done. These epoxy resins may be substituted with substituents having no adverse effects, such as alkyl groups and aryl groups. These epoxy resins may be used in combination of multiple types. Among these, epoxy resins having a divalent group represented by the above formula (3) are preferred.

In the case of the two-step method, a catalyst can be used, and any compound can be used as long as it has a catalytic ability to promote the reaction between the epoxy group and the phenolic hydroxyl group. Examples thereof include alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like. These catalysts may be used alone or in combination of two or more.

Examples of alkali metal compounds 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; and alkali metal alkoxides such as 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.

Examples of organic phosphorus compounds include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, trimethylcyclohexylphosphonium chloride, and trimethylcyclohexyl. phosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, triphenylethylphosphonium iodide, triphenylbenzylphosphonium chloride, triphenylbenzylphosphonium bromide, and the like.

Tertiary amines include, for example, triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, tetramethylammonium bromide, propylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride, phenyltrimethylammonium chloride and the like. .

Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Phenylimidazole etc. are mentioned.

Cyclic amines include, for example, 1,4-diazabicyclo[2,2,2]octane (DABCO), 1,8-diazabicyclo[5,4,0]-7-undecene (DBU), 1,5-diazabicyclo [4,3,0]-5-nonene (DBN), tetrahydro-1,4-(morpholine), N-methylmorpholine, N,N-dimethylaminopyridine (DMAP) and the like.

The amount of catalyst used is usually 0.001 to 1% by mass based on the reaction solid content. When an alkali metal compound is used as a catalyst, the alkali metal remains in the phenoxy resin and deteriorates the insulating properties of electronic/electrical parts and printed wiring boards using it. The total alkali metal content of such as is preferably 100 mass ppm or less, more preferably 60 mass ppm or less, and even more preferably 50 mass ppm or less. In addition, even when organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles, etc. are used as catalysts, they remain as catalyst residues in the phenoxy resin, similar to residual alkali metals. The content of phosphorus atoms or nitrogen atoms in the phenoxy resin is preferably 300 mass ppm or less, more preferably 200 mass ppm or less, and further preferably 100 mass ppm or less, because it deteriorates the insulating properties of electronic/electric parts and printed wiring boards. preferable.

In the case of the two-step method, a solvent may be used, and any solvent may be used as long as it dissolves the phenoxy resin and does not adversely affect the reaction. Examples thereof include aromatic hydrocarbons, ketones, ester solvents, ether solvents, amide solvents, glycol ether solvents and the like. These solvents may be used alone or in combination of two or more.

Examples of aromatic hydrocarbons include benzene, toluene, and xylene.

Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclopentanone, cyclohexanone and acetylacetone.

Examples of ester solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, ethyl propionate, ethyl butyrate, butyl butyrate, valerolactone, butyrolactone and the like.

Examples of ether solvents include diethyl ether, dibutyl ether, t-butyl methyl ether, tetrahydrofuran, dioxane and the like.

Examples of amide solvents include formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.

Glycol ether solvents include, for example, 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.

The amount of the solvent to be used can be appropriately selected according to the reaction conditions. Further, when a highly viscous product is produced during the reaction, the solvent can be added during the reaction to continue the reaction. After completion of the reaction, the solvent can be removed by distillation or the like, if necessary, or can be further added.

The reaction temperature in the case of the two-step method is such that the catalyst used does not decompose. If the reaction temperature is too high, the resulting phenoxy resin may deteriorate. Therefore, the reaction temperature is preferably 50 to 230°C, more preferably 100 to 210°C, even more preferably 120 to 200°C. The reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. When using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by using an autoclave to carry out the reaction under high pressure. When the heat of reaction needs to be removed, it is usually carried out by evaporation, condensation, reflux of the solvent used by the heat of reaction, indirect cooling, or a combination thereof.

The epoxy equivalent (g/eq.) of the phenoxy resin of the present invention is not particularly limited, but is preferably 1,000 to 50,000, more preferably 3,000 to 30,000, and further 4,000 to 20,000. 5,000 to 15,000 are particularly preferred. If the epoxy equivalent is too low, the film-forming properties of the phenoxy resin, elongation during film molding, and flexibility may deteriorate. On the other hand, if the epoxy equivalent is too high, the reactivity during curing may deteriorate. Incidentally, the epoxy equivalent of the phenoxy resin is determined by the method described in Examples.

The phenoxy resin of the present invention itself is a flexible thermoplastic resin and can be used alone, but it can be made into a thermosetting resin composition by blending a cross-linking agent or a curable resin component. can.

Examples of cross-linking agents or curable resin components include epoxy resins, acrylic acid ester resins, phenol resins, melanin resins, urea resins, unsaturated polyester resins, alkyd resins, thermosetting polyimide resins, acid anhydride compounds, polyisocyanates. compounds and blocked isocyanate compounds. Among these, epoxy resins, phenolic resins, melanin resins, acid anhydride compounds, polyisocyanate compounds and blocked isocyanate compounds are preferred, and bifunctional or higher functional epoxy resins, epoxy resin curing agents and curing accelerators are more preferred. These crosslinking agents or curable resin components may be used alone, or two or more of them may be used in combination.

The curable resin component is, for example, a resin composition that cures an epoxy resin with a curing agent, a resin composition that cures an acrylic acid ester resin with a radical polymerization initiator, a phenol resin, a resin component that self-polymerizes a melanin resin, etc. with heat. Examples of cross-linking agents include compounds capable of undergoing addition polymerization with secondary alcoholic hydroxyl groups of phenoxy resins, such as acid anhydride compounds, polyisocyanate compounds, and blocked isocyanate compounds.

The amount of the cross-linking agent or curable resin component is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, more preferably 25/75 to 99/1, as the phenoxy resin/curable resin component (mass ratio). 75/25 is more preferred. By blending a curable resin component, a material with even better heat resistance can be obtained.

When the curable resin component is an epoxy resin, conventionally known epoxy resins can be used. The epoxy resin refers to an epoxy resin having at least one epoxy group, preferably an epoxy resin having two or more epoxy groups, and more preferably an epoxy resin having three or more epoxy groups. Specific examples include polyglycidyl ether compounds, polyglycidylamine compounds, polyglycidyl ester compounds, alicyclic epoxy compounds, and other modified epoxy resins. These epoxy resins may be used alone, or two or more of the same epoxy resins may be used in combination, or different epoxy resins may be used in combination.

Specific examples of polyglycidyl ether compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, biphenol type epoxy resin, hydroquinone type epoxy resin, bisphenol fluorene type epoxy resin, and naphthalene diol. type epoxy resin, bisphenol S type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl ether type epoxy resin, resorcinol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, alkyl novolak type epoxy resin, styrenated phenol novolac type epoxy resin Resin, bisphenol novolak type epoxy resin, naphthol novolac type epoxy resin, β-naphthol aralkyl type epoxy resin, naphthalenediol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, biphenyl aralkyl phenol type epoxy resin, trihydroxyphenylmethane type epoxy resins, tetrahydroxyphenylethane-type epoxy resins, dicyclopentadiene-type epoxy resins, alkylene glycol-type epoxy resins, aliphatic cyclic epoxy resins, and the like.

Specific examples of polyglycidylamine compounds include diaminodiphenylmethane-type epoxy resins, meta-xylenediamine-type epoxy resins, 1,3-bisaminomethylcyclohexane-type epoxy resins, isocyanurate-type epoxy resins, aniline-type epoxy resins, and hydantoin-type epoxy resins. Epoxy resins, aminophenol-type epoxy resins, and the like are included.

Specific examples of polyglycidyl ester compounds include dimer acid type epoxy resins, hexahydrophthalic acid type epoxy resins, and trimellitic acid type epoxy resins.

Alicyclic epoxy compounds include aliphatic cyclic epoxy resins such as Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd.).

Specific examples of other modified epoxy resins include urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins, epoxy-modified polybutadiene rubber derivatives, carboxyl group-terminated butadiene nitrile rubber (CTBN)-modified epoxy resins, polyvinylarene polyoxide (for example, divinyl benzene dioxide, trivinylnaphthalene trioxide, etc.), phenoxy resins, and the like.

When blending an epoxy resin, it also contains a curing agent. A curing agent is a substance that contributes to a cross-linking reaction and/or a chain extension reaction between epoxy groups of an epoxy resin.

The amount of the curing agent is 0.1 to 100 parts by mass, preferably 1 to 80 parts by mass, more preferably 5 to 60 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the epoxy resin. 60 parts by mass is more preferable.

There are no particular restrictions on the curing agent, and any one generally known as an epoxy resin curing agent can be used. Phenolic curing agents, amide curing agents and imidazoles are preferred from the viewpoint of enhancing heat resistance. Active ester curing agents are preferred from the viewpoint of lowering water absorbency. In addition, amine curing agents, acid anhydride curing agents, organic phosphines, phosphonium salts, benzo compounds, tetraphenyl boron salts, organic acid dihydrazides, halogenated boron amine complexes, polymercaptan curing agents, isocyanate curing agents , blocked isocyanate-based curing agents, and the like. These curing agents may be used alone, or two or more of the same type may be used in combination, or other types may be used in combination.

Examples of phenolic curing agents include bisphenol A, bisphenol F, dihydroxydiphenylmethane, dihydroxydiphenyl ether, bis(hydroxyphenoxy)benzene, dihydroxydiphenyl sulfide, dihydroxydiphenyl ketone, dihydroxydiphenyl sulfone, fluorene bisphenol, hydroquinone, resorcinol, catechol, t Dihydric phenol compounds such as -butylcatechol, t-butylhydroquinone, dihydroxynaphthalene, dihydroxymethylnaphthalene, phenol novolak, bisphenol A novolak, cresol novolak, xylenol novolak, trishydroxyphenylmethane novolak, dicyclopentadiene phenol, naphthol novolak , styrenated phenol novolak, terpene phenol, heavy oil modified phenol, phenol aralkyl, naphthol aralkyl, polyhydroxystyrene, fluoroglycinol, pyrogallol, t-butylpyrogallol, benzenetriol, trihydroxynaphthalene, trihydroxybenzophenone, trihydroxyacetophenone trihydric or higher phenol compounds such as and phosphorus-containing phenol compounds such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide. Curing agents obtained by reacting these phenol compounds with indene or styrene may also be used. The phenol-based curing agent is preferably used in a molar ratio of active hydroxyl groups in the curing agent to epoxy groups in the epoxy resin within a range of 0.8 to 1.5.

Examples of amide curing agents include dicyandiamide and derivatives thereof, and polyamide resins. The amide curing agent is preferably used in a range of 0.1 to 25 parts by mass with respect to 100 parts by mass of the total epoxy resin component.

The imidazoles are not particularly limited as long as they are compounds having an imidazole skeleton. For example, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-un Decylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'- methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4 -diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2 -Phenyl-4-methyl-5-hydroxymethylimidazole, adducts of epoxy resins and the above imidazoles, and the like. Imidazoles are preferably used in an amount of 0.1 to 25 parts by weight per 100 parts by weight of the total epoxy resin component. In addition, since imidazoles have catalytic activity, they are generally classified as curing accelerators, which will be described later.

Active ester curing agents include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. Among them, phenol esters obtained by reacting a polyfunctional phenol compound and aromatic carboxylic acids as described in Japanese Patent No. 5152445 are more preferable. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of aromatic compounds having a phenolic hydroxyl group include catechol, dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadienyldiphenol, and phenol novolak. Commercially available products include Epiclon HPC-8000-65T (manufactured by DIC Corporation) and the like, but are not limited to these. The active ester curing agent is preferably used in a molar ratio of active ester groups in the curing agent to epoxy groups in the resin composition in the range of 0.2 to 2.0.

Examples of amine curing agents include diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, Examples include amine compounds such as polyamidoamine, which are condensates of acids such as dicyandiamide and dimer acid, and polyamines. The amine curing agent is preferably used in a molar ratio of active hydrogen groups in the curing agent to epoxy groups in the resin composition within a range of 0.5 to 1.5.

Acid anhydride curing agents include, for example, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, methyl anhydride nadic acid, maleic anhydride, and the like. The acid anhydride curing agent is preferably used in a molar ratio of acid anhydride groups in the curing agent to epoxy groups in the resin composition in the range of 0.5 to 1.5.

The active hydrogen group includes a functional group having an active hydrogen reactive with an epoxy group (a functional group having a latent active hydrogen that generates an active hydrogen by hydrolysis or the like, and a functional group that exhibits an equivalent curing action. ), and specific examples thereof include an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, and the like. Regarding active hydrogen groups, carboxyl group (--COOH) and phenolic hydroxyl group (--OH) are calculated as 1 mol, and amino group (--NH ₂ ) as 2 mol. Moreover, when the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, by reacting a monoepoxy resin with a known epoxy equivalent such as phenyl glycidyl ether with a curing agent with an unknown active hydrogen equivalent and measuring the amount of monoepoxy resin consumed, the active hydrogen equivalent of the curing agent used can be asked for.

Moreover, when mix|blending an epoxy resin, a hardening accelerator can be used as needed. Examples of curing accelerators include imidazoles, tertiary amines, phosphorus compounds such as phosphines, metal compounds, Lewis acids, and amine complex salts. These curing accelerators may be used alone or in combination of two or more.

The imidazoles are not particularly limited as long as they are compounds having an imidazole skeleton. For example, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, 1-methyl-2-ethylimidazole, 2-isopropylimidazole, 2,4- Alkyl-substituted imidazole compounds such as dimethylimidazole and 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole, 1- Aryl groups such as benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1-(2′-cyanoethyl)imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and an imidazole compound substituted with a hydrocarbon group containing a ring structure such as an aralkyl group.

Examples of tertiary amines include 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, 1,8-diaza-bicyclo[5.4.0]-7-undecene ( DBU) and the like.

Phosphines include, for example, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine and triphenylborane.

Examples of metal compounds include tin octylate.

Amine complex salts include, for example, boron trifluoride monoethylamine complex, boron trifluoride diethylamine complex, boron trifluoride isopropylamine complex, boron trifluoride chlorophenylamine complex, boron trifluoride benzylamine complex, and boron trifluoride. Examples include boron trifluoride complexes such as aniline complexes or mixtures thereof.

Among these curing accelerators, 2-dimethylaminopyridine, 4-dimethylaminopyridine and Imidazoles are preferred.

The amount of the curing accelerator to be blended may be appropriately selected according to the purpose of use. 0.01 to 10 parts by mass is preferable, 0.05 to 8 parts by mass is more preferable, and 0.1 to 5 parts by mass is even more preferable. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

A resin composition in which an acrylic acid ester resin as a curable resin component is cured with a radical polymerization initiator includes a thermosetting resin composition and a photocurable resin composition of a (meth)acrylate compound. A (meth)acrylate compound is an acrylate having at least one (meth)acryloyl group in the molecule, which is used for viscosity adjustment or as a curing component. A portion of the (meth)acrylate compound preferably has two or more (meth)acryloyl groups. The resin composition in this case contains a (meth)acrylate compound, a thermal polymerization initiator, a photopolymerization initiator, or both as essential components.

These (meth)acrylate compounds include monofunctional (meth)acrylic acid esters, polyfunctional (meth)acrylates, urethane (meth)acrylates, epoxy acrylates, and the like. These (meth)acrylate compounds may be used alone, or two or more of them may be used in combination.

Monofunctional (meth)acrylic acid esters include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl ( meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Cyclohexane-1,4-dimethanol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) ) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-cumylphenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, tribromophenyloxyethyl (meth) Acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate and the like.

Polyfunctional (meth)acrylates include, for example, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, bisphenol A Polyethoxydi(meth)acrylate, bisphenol A polypropoxydi(meth)acrylate, bisphenol F polyethoxydi(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, tris(acryloxyethyl) isocyanurate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, neopentylglycol hydroxybivalate di(meth)acrylate, trimethylol propane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, cyclohexanedimethanol di(meth)acrylate and dimethyloltricyclodecane di(meth)acrylate and the like. .

A urethane (meth)acrylate can be obtained by reacting a polyol compound with a polyisocyanate compound and further reacting with (meth)acrylate. Epoxy acrylates are obtained by the reaction of epoxy compounds and (meth)acrylates.

In addition, the compound that can be used as a polymerization initiator for the (meth)acrylate compound is not particularly limited as long as it generates radicals by means of heating, irradiation with active energy ray light, or the like. . As the polymerization initiator, for example, when curing is performed by heating, any azo-based initiator such as azobisisobutyronitrile, benzoyl peroxide, or a peroxide-based initiator that can be used for normal radical thermal polymerization can be used. can be used. When radical polymerization is carried out by photo-radical polymerization, any of benzoins, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, phosphine oxides, etc. that can be used for ordinary photo-radical polymerization should be used. can be done. These polymerization photoinitiators may be used alone or as a mixture of two or more. Furthermore, the photoradical polymerization initiator may be used in combination with a tertiary amine compound, an accelerator such as N,N-dimethylaminobenzoic acid ethyl ester, or the like.

Moreover, an organic solvent or a reactive diluent can be used in the resin composition of the present invention for viscosity adjustment. These organic solvents or reactive diluents may be used alone or in combination of two or more.

Examples of organic solvents include amides such as N,N-dimethylformamide and N,N-dimethylacetamide, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol. Ethers such as dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol , butyl diglycol, pine oil and other alcohols, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate, etc. Acetic esters, benzoic acid esters such as methyl benzoate and ethyl benzoate, cellosolves such as methyl cellosolve, cellosolve, and butyl cellosolve, carbitols such as methyl carbitol, carbitol, and butyl carbitol, and benzene , toluene and xylene, sulfoxides such as dimethylsulfoxide, alkanes such as hexane and cyclohexane, acetonitrile, and N-methylpyrrolidone.

Examples of reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, resorcinol diglycidyl ether, and neopentyl glycol diglycidyl ether. , 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, propylene glycol diglycidyl ether and other bifunctional glycidyl ethers, glycerol polyglycidyl ether, trimethylolpropane Polyfunctional glycidyl ethers such as polyglycidyl ether, trimethylolethane polyglycidyl ether, and pentaerythritol polyglycidyl ether; glycidyl esters such as neodecanoic acid glycidyl ester; and glycidylamines such as phenyldiglycidylamine and tolyldiglycidylamine. is mentioned.

These organic solvents or reactive diluents are preferably used at a non-volatile content of 90% by mass or less, and the appropriate type and amount to be used are appropriately selected depending on the application. For example, for printed wiring board applications, a polar solvent having a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, or 1-methoxy-2-propanol, is preferred, and the amount used is preferably 40 to 80% by mass in terms of non-volatile matter. In addition, for adhesive film applications, for example, it is preferable to use ketones, acetic esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and the amount used is nonvolatile is preferably 30 to 60% by mass.

Various known flame retardants can be used in the resin composition of the present invention for the purpose of improving the flame retardancy of the resulting cured product, as long as the reliability is not lowered. Usable flame retardants include, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. From an environmental point of view, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used alone, or two or more flame retardants of the same type may be used in combination, or flame retardants of different types may be used in combination.

Phosphorus-based flame retardants are divided into two types: additive-based phosphorus-based flame retardants (phosphorus-containing additives) and reactive phosphorus compounds. Reactive phosphorus compounds are further divided into phosphorus-containing epoxy resins and phosphorus-containing curing agents. divided. Comparing additive-based phosphorus-based flame retardants with reactive phosphorus compounds, reactive phosphorus compounds do not bleed out during curing and have good compatibility. It is preferred to use a phosphorus compound of

As the phosphorus-containing additive, both inorganic phosphorus compounds and organic phosphorus compounds can be used. Examples of inorganic phosphorus compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as amide phosphoric acid. but not limited to these.

In addition, red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis, etc. Examples of surface treatment methods include (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, hydroxide (2) Inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and phenolic resins. (3) Coating with a thermosetting resin such as phenol resin on a coating of inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. Examples include a double coating method and the like, but are not limited to these.

Examples of organic phosphorus compounds include phosphoric acid ester compounds (e.g., methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2- ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, butyl pyrophosphate, ethylene glycol acid phosphate, (2- hydroxyethyl) methacrylate acid phosphate, etc.), condensed phosphate esters (e.g., PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), etc.), phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds (e.g., diphenylphosphine oxide, triphenylphosphine oxide, etc.), general-purpose organic phosphorus compounds such as phosphorane compounds (e.g., triphenyl (9H-fluorene-9-ylidene) phosphorane, etc.), and nitrogen-containing organic phosphorus compounds (e.g., SPS-100, SPB- 100, SPE-100 (manufactured by Otsuka Chemical Co., Ltd., etc.), metal phosphinic acid salts (e.g., EXOLIT OP1230, OP1240, OP930, OP935 (manufactured by Clariant Co., Ltd.), etc.), and directly linked to the phosphorus atom Phosphorus compounds having an active hydrogen group (e.g., 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO), diphenylphosphine oxide, etc.) and phosphorus-containing phenol compounds (e.g., 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as DOPO-HQ), 10-(2,7-dihydroxy-1-naphthyl)- 10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dihydroxy-2-naphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, DOPO- NQ), diphenylphosphinylhydroquinone, diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyl 1,5-cyclooctylenephosphinyl-1,4-phenyldiol, etc.), but not limited thereto.

Also included are phosphorus-containing epoxy resins and phosphorus-containing curing agents, which are derivatives obtained by reacting the above organic phosphorus compounds with compounds such as epoxy resins and phenolic resins. As the reactive phosphorus compound used for these, the above phosphorus compound having an active hydrogen group directly attached to the phosphorus atom and phosphorus-containing phenols are preferable. is more preferred.

Phosphorus-containing epoxy resins include, for example, Epotato FX-305, FX-289B, FX-1225, TX-1320A, TX-1328 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), etc., but limited to these. not to be

The epoxy equivalent of the phosphorus-containing epoxy resin is preferably 200-800, more preferably 300-780, and even more preferably 400-760. The phosphorus content of the phosphorus-containing epoxy resin is preferably 0.5 to 6% by mass, more preferably 2 to 5.5% by mass, even more preferably 3 to 5% by mass.

As the phosphorus-containing curing agent, in addition to the above-mentioned phosphorus-containing phenols, for example, DOPO, aldehydes and phenol compounds are reacted by the production method shown in Japanese Patent Publication No. 2008-501063 and Japanese Patent No. 4548547. By doing so, a phosphorus-containing phenol compound can be obtained. In this case, the phosphorus compound is incorporated into the molecule by condensing addition to the aromatic ring of the phenol compound via the aldehyde. Further, a phosphorus-containing active ester compound can be obtained from a phosphorus-containing phenol compound by further reacting it with an aromatic carboxylic acid by a production method as shown in JP-A-2013-185002. Further, a phosphorus-containing benzo compound can be obtained by a production method as shown in Japanese Patent Re-publication WO2008/010429.

The phosphorus content of the phosphorus-containing curing agent is preferably 0.5 to 12% by mass, more preferably 2 to 11% by mass, and even more preferably 4 to 10% by mass.

The amount of the phosphorus compound to be blended is appropriately selected depending on the type of phosphorus compound, the components of the resin composition, and the desired degree of flame retardancy. When the phosphorus compound is a reactive phosphorus compound, that is, a phosphorus-containing epoxy resin or a phosphorus-containing curing agent, the phosphorus content is 0.2 to 6% by mass relative to the solid content (non-volatile content) in the resin composition. is preferred, 0.4 to 4% by mass is more preferred, 0.5 to 3.5% by mass is even more preferred, and 0.6 to 3% by mass is particularly preferred. If the phosphorus content is too low, it may become difficult to ensure flame retardancy, and if it is too high, heat resistance may be adversely affected.

When a phosphorus-based flame retardant is used, flame retardant aids such as hydrotalcite, magnesium hydroxide, boron compounds, zirconium oxide, calcium carbonate, and zinc molybdate may be used in combination.

Nitrogen-based flame retardants include, for example, triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine and the like, with triazine compounds, cyanuric acid compounds and isocyanuric acid compounds being preferred. The amount of the nitrogen-based flame retardant compounded is appropriately selected depending on the type of nitrogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. (Non-volatile content) It is preferable to blend in the range of 0.05 to 10 parts by mass, particularly preferably in the range of 0.1 to 5 parts by mass in 100 parts by mass. Moreover, when using a nitrogen flame retardant, a metal hydroxide, a molybdenum compound, etc. may be used together.

Examples of triazine compounds include melamine, acetoguanamine, benzoguanamine, melon [2,4,6-tris(cyanoamino)-1,3,5-triazine], melam [4,4′-iminobis(1,3,5 -triazine-2,6-diamine)], ethylenedimelamine, melamine polyphosphate, triguanamine, etc., aminotriazine sulfate compounds such as guanylmelamine sulfate, melem sulfate, and melam sulfate, aminotriazine-modified phenolic resins (for example, , LA-7052 (manufactured by DIC Corporation), and aminotriazine-modified phenolic resins further modified with tung oil, isomerized linseed oil, etc., but not limited thereto.

Examples of the cyanuric acid compound include cyanuric acid and melamine cyanurate, but are not limited thereto.

As the silicone flame retardant, any organic compound containing a silicon atom can be used without any particular limitation. Examples thereof include silicone oil, silicone rubber, and silicone resin, but are not limited to these. The amount of the silicone-based flame retardant compounded is appropriately selected depending on the type of the silicone-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. (Non-volatile content) It is preferable to blend in the range of 0.05 to 20 parts by mass in 100 parts by mass. Moreover, when using a silicone-type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

Examples of inorganic flame retardants include, but are not limited to, metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. The amount of the inorganic flame retardant compounded is appropriately selected depending on the type of inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. Non-volatile matter) is preferably blended in the range of 0.05 to 20 parts by mass, particularly preferably in the range of 0.5 to 15 parts by mass per 100 parts by mass.

Examples of metal hydroxides include, but are not limited to, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, boehmite, calcium hydroxide, barium hydroxide, zirconium hydroxide, and the like. .

Examples of metal oxides include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples include, but are not limited to, chromium oxide, nickel oxide, copper oxide, tungsten oxide, and the like.

Examples of metal carbonate compounds include, but are not limited to, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate. do not have.

Metal powders include, but are not limited to, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

Examples of boron compounds include, but are not limited to, zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Examples of low-melting glass include hydrated glass, SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O ₅ —B ₂ O ₃ —PbO. -MgO-based, PSn-OF-based, PbO-V ₂ O ₅ -TeO ₂ -based, Al ₂ O ₃ -H ₂ O-based, and lead borosilicate-based glassy compounds, but are not limited to these. not something.

The amount of the inorganic flame retardant compounded is appropriately selected depending on the type of inorganic flame retardant, other components of the resin composition, and the desired degree of flame retardancy. Non-volatile matter) is preferably blended in the range of 0.05 to 20 parts by mass, particularly preferably in the range of 0.5 to 15 parts by mass per 100 parts by mass.

Examples of organic metal salt flame retardants include ferrocene, acetylacetonate metal complexes, organic metal carbonyl compounds, organic cobalt salt compounds, organic sulfonic acid metal salts, metal atoms and aromatic compounds or heterocyclic compounds in ionic bonds or coordination. Examples include, but are not limited to, positionally bonded compounds. The amount of the organometallic salt-based flame retardant to be blended is appropriately selected depending on the type of the organometallic salt-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. It is preferable to blend in the range of 0.005 to 10 parts by mass based on 100 parts by mass of the solid content (non-volatile content).

Halogen-based flame retardants include bromine compounds and chlorine compounds, but chlorine compounds are not preferred due to toxicity problems. The amount of the halogen-based flame retardant compounded is appropriately selected depending on the type of halogen-based flame retardant, other components of the resin composition, and the desired degree of flame retardancy. The halogen content is preferably 5 to 15% by mass based on the (non-volatile content).

In addition, when a halogen-based flame retardant is used as a flame retardant, flame retardant aids include, for example, antimony compounds such as antimony trioxide, antimony tetroxide, and antimony pentoxide; and tin compounds such as tin oxide and tin hydroxide. , molybdenum compounds such as molybdenum oxide and ammonium molybdate, zirconium compounds such as zirconium oxide and zirconium hydroxide, boron compounds such as zinc borate and barium metaborate, silicone oils, silane coupling agents, high molecular weight silicones, etc. A silicon-based compound, chlorinated polyethylene, or the like may be used in combination.

Bromine compounds include, for example, p-dibromobenzene, pentabromodiphenyl ether, octabromodiphenyl ether, tetradecabromo-p-diphenoxybenzene, decabromodiphenyl ether, tetrabromobisphenol A, hexabromocyclododecane, hexabromobenzene, 2, 2′-ethylenebis(4,5,6,7-tetrabromoisoindoline-1,3-dione (eg, SAYTEX BT-93 (manufactured by Albemarle), etc.), ethane-1,2-bis(penta bromophenyl) (e.g., SAYTEX 8010 (manufactured by Albemarle), etc.) and brominated epoxy oligomers (e.g., SR-T1000, SR-T2000 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), etc.), and the like. is not limited to

In addition, if necessary, the resin composition may contain fillers, thermoplastic resins, coupling agents, antioxidants, release agents, antifoaming agents, emulsifiers, thixotropic agents, as long as the properties are not impaired. Other additives such as leveling agents, pigments, etc. can be incorporated.

Examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, Barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, inorganic fillers such as carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide Examples include fibrous fillers such as fibers, polyester fibers, cellulose fibers, aramid fibers and ceramic fibers, and fine particle rubbers.

Among these, those that are not decomposed or dissolved by oxidizing compounds such as permanganate aqueous solutions used for surface roughening treatment of cured products are preferred, and fused silica and crystalline silica are particularly easy to obtain fine particles. preferable. Further, it is preferable to use fused silica when the compounding amount of the filler is particularly large. Either crushed or spherical fused silica can be used, but it is more preferable to mainly use spherical fused silica in order to suppress an increase in the melt viscosity of the molding material while increasing the blending amount of fused silica. . Furthermore, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filler may be treated with a silane coupling agent or treated with an organic acid such as stearic acid. Reasons for using a filler in general include the effect of improving the impact resistance of the cured product and lowering the linear expansion of the cured product. Moreover, when metal hydroxides such as aluminum hydroxide, boehmite and magnesium hydroxide are used, they act as flame retardant aids and have the effect of improving flame retardancy. When improving thermal conductivity, alumina, silicon nitride, boron nitride, aluminum nitride, fused silica, and crystalline silica are preferable, and alumina, boron nitride, fused silica, and crystalline silica are more preferable. When used as a conductive paste, a conductive filler such as silver powder or copper powder can be used.

The amount of the filler compounded is preferably as high as possible in consideration of low linear expansion and flame retardancy of the cured product. It is preferably 1 to 98% by mass, more preferably 3 to 90% by mass, even more preferably 5 to 80% by mass, and particularly preferably 10 to 60% by mass, based on the total solid content in the resin composition. If the compounding amount is too large, there is a risk that the adhesiveness required for use as a laminate will be lowered, and furthermore, the cured product will be brittle, and there is a risk that sufficient mechanical properties will not be obtained. On the other hand, if the blending amount is too small, there is a fear that the blending effect of the filler, such as improving the impact resistance of the cured product, may not be achieved.

In addition, if the particle size of the inorganic filler is too large, voids tend to remain in the cured product. The average particle size is preferably 0.01 to 5 μm, more preferably 0.05 to 1.5 μm, even more preferably 0.1 to 1 μm. If the average particle size of the inorganic filler is within this range, the fluidity of the resin composition can be maintained well. The average particle size can be measured using a particle size distribution analyzer.

A thermoplastic resin other than the phenoxy resin of the present invention may be used in combination with the resin composition of the present invention. Examples of thermoplastic resins include phenoxy resins other than the present invention, polyurethane resins, polyester resins, polyethylene resins, polypropylene resins, polystyrene resins, ABS resins, AS resins, vinyl chloride resins, polyvinyl acetate resins, and polymethyl methacrylate resins. , polycarbonate resin, polyacetal resin, cyclic polyolefin resin, polyamide resin, thermoplastic polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyethersulfone resin, polysulfone resin , polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formal resin, and the like. Phenoxy resins other than those of the present invention are preferred from the viewpoint of compatibility, and polyphenylene ether resins and modified polyphenylene ether resins are preferred from the viewpoint of low dielectric properties.

A coupling agent may be added to the resin composition of the present invention. By blending the coupling agent, the adhesiveness to the substrate and the adhesiveness between the matrix resin and the inorganic filler can be improved. Examples of coupling agents include silane coupling agents and titanate coupling agents. These coupling agents may be used alone or in combination of two or more. The amount of the coupling agent compounded is preferably about 0.1 to 2.0% by mass with respect to the total solid content in the resin composition. If the amount of the coupling agent is too small, the effect of improving the adhesion between the matrix resin and the inorganic filler due to the addition of the coupling agent cannot be sufficiently obtained. If it is too long, the coupling agent may bleed out from the resulting cured product.

Examples of silane coupling agents include epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ- Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxy aminosilanes such as silane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacrylic Examples include vinylsilanes such as roxypropyltrimethoxysilane, epoxy-based, amino-based, and vinyl-based high-molecular-type silanes.

Examples of titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl/aminoethyl) titanate, diisopropyl bis(dioctylphosphate) titanate, tetraisopropyl bis(dioctylphosphite) titanate, tetraoctyl bis ( ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate and the like. be done.

Other additives include organic pigments such as quinacridones, azos, and phthalocyanines, inorganic pigments such as titanium oxide, metal foil pigments, and antirust pigments, and ultraviolet rays such as hindered amines, benzotriazoles, and benzophenones. Absorbents, hindered phenol-based, phosphorus-based, sulfur-based, hydrazide-based antioxidants, release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, leveling agents, rheology control agents, and pigments Additives such as a dispersant, an anti-cratering agent, and an antifoaming agent are included. The blending amount of these other additives is preferably in the range of 0.01 to 20% by mass based on the total solid content in the resin composition.

The resin composition of the present invention is obtained by uniformly mixing the above components. A resin composition containing a phenoxy resin, a curable resin component, and optionally various additives can be easily cured by a conventionally known method. Examples of cured products include molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films. As a method for obtaining a cured product, the same methods as those for known resin compositions can be used, such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, resin sheet, resin-coated copper. A method such as forming a laminated plate by laminating a foil, prepreg, or the like and curing under heat and pressure is preferably used. The method of curing the resin composition varies depending on the ingredients and amounts of the resin composition, but usually the curing temperature is 80 to 300° C. and the curing time is 10 to 360 minutes. This heating is preferably performed in a two-step process of primary heating at 80 to 180° C. for 10 to 90 minutes and secondary heating at 120 to 200° C. for 60 to 150 minutes. In a compounded system that exceeds the secondary heating temperature, it is preferable to further perform tertiary heating at 150 to 280° C. for 60 to 120 minutes. By performing such secondary heating and tertiary heating, poor curing can be reduced. When semi-cured resin products such as resin sheets, resin-coated copper foils, and prepregs are produced, the curing reaction of the resin composition is usually allowed to proceed by heating or the like to such an extent that the shape can be maintained. When the resin composition contains a solvent, most of the solvent is usually removed by heating, depressurization, air drying, or the like. good too.

Applications in which the resin composition is used include circuit board materials, sealing materials, casting materials, conductive pastes, adhesives, insulating materials, etc., and can be applied to various fields, particularly in the electrical and electronic fields. It is useful as an insulating casting, lamination material, sealing material, etc. Examples of applications include printed wiring boards, flexible wiring boards, laminates for electrical and electronic circuits such as capacitors, metal foils with resin, film adhesives, adhesives such as liquid adhesives, semiconductor sealing materials, underlays, etc. Fill materials, inter-chip fills for 3D-LSI, insulating materials for circuit boards, insulating sheets, prepregs, heat-dissipating substrates, resist inks, but are not limited to these.

Among these various applications, printed wiring board materials, insulating materials for circuit boards, and adhesive film applications for build-up are so-called substrates for embedding electronic components, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. It can be used as an insulating material for Among these, materials for circuit boards (laminates) such as printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulation materials for build-up boards, due to their properties such as high flame retardancy, high heat resistance and solvent solubility and semiconductor encapsulating materials.

When the resin composition is formed into a plate such as a laminated plate, the filler to be used is preferably fibrous from the viewpoint of its dimensional stability, bending strength, etc. Examples thereof include glass cloth, glass mat, and glass roving cloth. more preferred.

By impregnating a fibrous reinforcing base material with the resin composition, a prepreg used in printed wiring boards and the like can be produced. As the fibrous reinforcing substrate, for example, inorganic fibers such as glass, and woven or non-woven fabrics of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, aromatic polyamide resin, etc. can be used. It is possible, but not limited to this.

The method for producing a prepreg from a resin composition is not particularly limited. For example, the varnish-like resin composition containing the above organic solvent is further blended with an organic solvent to adjust the viscosity to an appropriate resin varnish. After impregnating the fibrous base material with the resin varnish, the resin component is semi-cured (B-staged) by heating and drying. The heating temperature is preferably 50 to 200°C, more preferably 100 to 170°C, depending on the type of organic solvent used. The heating time is adjusted according to the type of organic solvent used and the curability of the prepreg, preferably 1 to 40 minutes, more preferably 3 to 20 minutes. In this case, the mass ratio of the resin composition and the reinforcing base material to be used is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to 20 to 80 mass %.

The resin composition of the present invention can be used after being molded into a sheet or film. In this case, it is possible to form a sheet or film using a conventionally known method. The method for producing a resin sheet is not particularly limited, but for example, (a) extrusion after kneading the resin composition with an extruder and molding it into a sheet using a T die, a circular die, etc. (b) a casting molding method in which a resin composition is dissolved or dispersed in a solvent such as an organic solvent and then cast into a sheet, and (c) other conventionally known sheet molding methods. . The film thickness (μm) of the resin sheet is not particularly limited, but is preferably 10-300, more preferably 25-200, and even more preferably 40-180. The film thickness of the resin sheet used in the build-up method is particularly preferably 40 to 90 μm. If the film thickness is 10 μm or more, insulation can be obtained, and if the film thickness is 300 μm or less, the circuit distance between the electrodes will not be longer than necessary. Although the content of the solvent in the resin sheet is not particularly limited, it is preferably 0.01 to 5% by mass with respect to the entire 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 easily obtained when laminating to a circuit board, and if it is 5% by mass or less, heating It is easy to obtain flatness after curing.

As a more specific method for producing an adhesive sheet, a coating machine such as a reverse roll coater, a comma coater, a die coater, or the like is used to apply the varnish-like resin composition containing the above organic solvent onto a supporting base film insoluble in an organic solvent. It is obtained by heating and drying the resin component to the B-stage after applying the resin. In addition, if necessary, another supporting base film is laminated as a protective film on the coated surface (adhesive layer) and dried to obtain an adhesive sheet having release layers on both sides of the adhesive layer.

Examples of the supporting base film include metal foil such as copper foil, polyolefin film such as polyethylene film and polypropylene film, polyester film such as polyethylene terephthalate film, polycarbonate film, silicon film, polyimide film, and the like. A polyethylene terephthalate film is preferable because it has no defects, has excellent dimensional accuracy, and is excellent in terms of cost. A metal foil, particularly a copper foil, is preferred because it facilitates multi-layering of the laminate. The thickness of the support base film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm, because it has strength as a support and is less prone to lamination defects.

Although the thickness of the protective film is not particularly limited, it is generally 5 to 50 μm. In addition, in order to easily peel off the molded adhesive sheet, it is preferable to perform a surface treatment with a release agent in advance. The thickness of the resin varnish applied is preferably 5 to 200 μm, more preferably 5 to 100 μm, in terms of thickness after drying.

The heating temperature is preferably 50 to 200°C, more preferably 100 to 170°C, depending on the type of organic solvent used. The heating time is adjusted according to the type of organic solvent used and the curability of the prepreg, preferably 1 to 40 minutes, more preferably 3 to 20 minutes.

The resin sheet thus obtained is usually an insulating adhesive sheet having insulating properties. By mixing a resin composition with a conductive metal or metal-coated fine particles, a conductive adhesive sheet can be obtained. can also The supporting base film is peeled off after being laminated on the circuit board or after being cured by heating to form an insulating layer. If the supporting base film is peeled off after the adhesive sheet is cured by heating, it is possible to prevent the adhesion of dust and the like during the curing process. Here, the insulating adhesive sheet is also an insulating sheet.

A resin-coated metal foil obtained from the resin composition of the present invention will be described. As the metal foil, copper, aluminum, brass, nickel, or the like can be used alone, as an alloy, or as a composite metal foil. A metal foil having a thickness of 9 to 70 μm is preferably used. The method for producing a resin-coated metal foil from the resin composition and the metal foil of the present invention is not particularly limited. After application using a roll coater or the like, the resin component is semi-cured (to B stage) by heating and drying to form a resin layer. In semi-curing the resin component, for example, it can be dried by heating at 100 to 200° C. for 1 to 40 minutes. Here, the thickness of the resin portion of the resin-coated metal foil is preferably 5 to 110 μm.

In order to cure the prepreg and the insulating adhesive sheet, a method of curing a laminate generally used in manufacturing a printed wiring board can be used, but the method is not limited to this. For example, when forming a laminate using prepreg, one or more prepregs are laminated, metal foil is arranged on one side or both sides to form a laminate, and this laminate is pressurized and heated. Thus, the prepreg can be cured and integrated to obtain a laminate. Here, as the metal foil, copper, aluminum, brass, nickel, or the like can be used alone, as an alloy, or as a composite metal foil.

The conditions for heating and pressurizing the laminate may be appropriately adjusted so as to cure the resin composition, but if the pressure applied is too low, air bubbles will remain inside the resulting laminate. However, since the electrical characteristics may deteriorate, it is preferable to apply pressure under conditions that satisfy moldability. The heating temperature is preferably 160 to 250°C, more preferably 170 to 220°C. The applied pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. If the heating temperature is too low, the curing reaction may not proceed sufficiently, and if the heating temperature is too high, the cured product may be thermally decomposed. If the applied pressure is too low, air bubbles may remain inside the obtained laminate and the electrical properties may deteriorate. There is fear. Also, if the heating and pressurizing time is short, the curing reaction may not proceed sufficiently, and if it is long, the cured product may be thermally decomposed.

Furthermore, a multi-layer board can be produced by using the single-layer laminate board thus obtained as an inner layer material. In this case, first, a circuit is formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is treated with an acid solution for blackening to obtain an inner layer material. An insulating layer is formed on one or both sides of the inner layer material using a prepreg, a resin sheet, an insulating adhesive sheet, or a metal foil with resin, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board. to form.

In addition, when forming an insulating layer using prepreg, one or more layers of prepreg are placed on the circuit forming surface of the inner layer material, and a metal foil is placed on the outer side to form a laminate. to form By heating and pressurizing this laminated body to integrally mold it, the cured prepreg is formed as an insulating layer, and the metal foil on the outside thereof is formed as a conductor layer. Here, as the metal foil, the same one as that used for the laminated plate used as the inner layer plate can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material. A printed wiring board can be molded by forming via holes and circuits on the surface of the multilayer laminate thus molded by an additive method or a subtractive method. Further, by repeating the above-described method using this printed wiring board as an inner layer material, a multilayer board having more layers can be formed.

For example, when forming the insulating layer with an insulating adhesive sheet, the insulating adhesive sheet is placed on the circuit forming surface of a plurality of inner layer materials to form a laminate. Alternatively, a laminate is formed by placing an insulating adhesive sheet between the circuit forming surface of the inner layer material and the metal foil. Then, this laminate is heated and pressurized for integral molding, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multi-layered inner layer material. Alternatively, the inner layer material and the metal foil, which is the conductor layer, are formed as an insulating layer by curing an insulating adhesive sheet. Here, as the metal foil, the same one as that used for the laminate used as the inner layer material can be used. Further, the heat and pressure molding can be performed under the same conditions as the molding of the inner layer material.

Further, when the resin composition is applied to the laminate to form the insulating layer, the resin composition is preferably applied to a thickness of 5 to 100 μm and then heated at 100 to 200° C., preferably 150 to 200° C. for 1 It is heated and dried for up to 120 minutes, preferably 30 to 90 minutes to form a sheet. It is formed by a method generally called a casting method. The thickness after drying is preferably 5 to 150 μm, preferably 5 to 80 μm. The viscosity of the resin composition is preferably 10 to 40,000 mPa·s, more preferably 200 to 30,000 mPa·s at 25° C., since a sufficient film thickness can be obtained and coating unevenness and streaks are less likely to occur. A printed wiring board can be formed by forming via holes and circuits on the surface of the multilayer laminate thus formed by an additive method or a subtractive method. Further, by repeating the above-described method using this printed wiring board as an inner layer material, a laminated board having more layers can be formed.

Sealing materials obtained by using the resin composition of the present invention include tape-shaped semiconductor chips, potting-type liquid sealing, underfill, semiconductor interlayer insulating films, and the like. can be used. For example, for molding a semiconductor package, a resin composition is molded using a casting or transfer molding machine, an injection molding machine, etc., and further heated at 50 to 200° C. for 2 to 10 hours to obtain a molded product. is mentioned.

In order to prepare a resin composition for use as a semiconductor encapsulating material, compounding agents such as inorganic fillers and additives such as coupling agents and release agents are added to the resin composition as necessary. After pre-mixing, a technique of sufficiently melt-mixing using an extruder, a kneader, a roll, or the like until the mixture becomes uniform can be used. At that time, silica is usually used as the inorganic filler, and in that case, it is preferable to blend the inorganic filler in a proportion of 70 to 95% by mass in the resin composition.

When the resin composition thus obtained is used as a tape-shaped encapsulant, it is heated to prepare a semi-cured sheet, which is made into an encapsulant tape, and then this encapsulant tape is used. It can be placed on a semiconductor chip, heated to 100 to 150.degree. When used as a potting-type liquid encapsulant, the obtained resin composition may be dissolved in a solvent if necessary, applied onto a semiconductor chip or an electronic component, and cured directly.

Moreover, the resin composition of the present invention can also be used as a resist ink. In this case, a vinyl-based monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are blended into the resin composition, and a pigment, talc and filler are added to prepare a resist ink composition. After that, after coating onto a printed board by a screen printing method, a method of forming a resist ink cured product may be mentioned. The curing temperature at this time is preferably in the temperature range of about 20 to 250.degree.

The resin composition of the present invention was prepared, and the cured product was evaluated by heat curing. This indicates that the material has excellent tracking resistance. Therefore, it is useful as a material for substrates on which heat-generating components such as LEDs are mounted.

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these as long as the gist thereof is not exceeded. Unless otherwise specified, parts represent "mass parts" and % represents "mass%". The analysis method and measurement method are shown below.

(1) epoxy equivalent:
The measurement was performed according to the JIS K7236 standard, and the unit was expressed as "g/eq.". Specifically, a potentiometric titrator was used, methyl ethyl ketone was used as a solvent, and a 0.1 mol/L perchloric acid-acetic acid solution was used by adding a tetraethylammonium bromide acetic acid solution. For the solvent-diluted product (resin varnish), the solid content conversion value was calculated from the non-volatile content.

(2) hydroxyl equivalent:
The measurement was performed according to the JIS K0070 standard, and the unit was expressed as "g/eq.". In addition, unless otherwise specified, the hydroxyl group equivalent of the phenolic resin means the phenolic hydroxyl group equivalent.

(3) non-volatile content:
It was measured according to JIS K7235 standard. The drying temperature was 200° C. and the drying time was 60 minutes.

(4) Weight average molecular weight (Mw):
Obtained by GPC measurement. Specifically, a column (manufactured by Tosoh Corporation, TSKgelG4000H _XL , TSKgelG3000H _XL , TSKgelG2000H _XL ) in series with a main body (manufactured by Tosoh Corporation, HLC-8220GPC) was used, and the column temperature was set to 40 ° C. . Tetrahydrofuran (THF) was used as an eluent at a flow rate of 1 mL/min, and a differential refractive index detector was used as a detector. A measurement sample was obtained by dissolving 0.05 g of the sample in 10 mL of THF and filtering through a microfilter, and used 50 μL of the solution. Standard monodisperse polystyrene (manufactured by Tosoh Corporation, A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40 , F-80, F-128). For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.

(5) Glass transition temperature (Tg):
IPC-TM-650 2.4.25. Measured according to the c standard. Specifically, it was represented by the extrapolated glass transition start temperature (Tig) of the DSC chart obtained in the second cycle of differential scanning calorimetry. EXSTAR6000 DSC6200 manufactured by SII Nanotechnology Co., Ltd. was used as a differential scanning calorimeter. A measurement sample was used by punching a resin film, laminating it, and packing it in an aluminum capsule. The measurement was carried out two cycles from room temperature to 280°C at a heating rate of 10°C/min.

(6) Thermal conductivity:
It was measured by the unsteady hot wire method using a NETZSCH LFA447 thermal conductivity meter.

(7) Solvent solubility:
After removing the solvent from the resin varnish in a vacuum oven under the conditions of 170 ° C. and 0.2 kPa for 1 hour, it is mixed with methyl ethyl ketone (MEK) and heated to 60 ° C. to dissolve completely, and the nonvolatile content is 30. % MEK lysate was obtained. Solvent solubility was determined by the presence or absence of turbidity in the MEK solution when cooled to room temperature. A transparent sample was rated as ◯, and a sample with even a little turbidity was rated as x.

(8) IR:
A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used to measure the absorbance at a wavenumber of 600 to 4000 cm ⁻¹ .

(9) Copper foil peel strength:
It was measured according to JIS C6481 standard.

(10) Moisture absorption rate:
Five 50 mm×50 mm square test pieces were cut out of the laminated plate with etched copper foil, and the measurement was performed. After drying the specimen for 24 hours at 125° C. in an air atmosphere using a hot air circulating oven, the weight was immediately measured. The test piece was stored in a treatment tank adjusted to a temperature of 85° C. and a humidity of 85% RH, and the moisture absorption rate was determined from the weight increase after 168 hours.

Abbreviations used in Examples and Comparative Examples are as follows.

[Epoxy resin]
E1: Epoxy resin of 2,5-di-t-butylhydroquinone (manufactured by Nippon Steel Chemical & Materials Co., Ltd., YDC-1312, epoxy equivalent 176)
E2: Hydroquinone epoxy resin (manufactured by Nippon Steel Chemical & Materials Co., Ltd., ZX-1027, epoxy equivalent 130)
E3: Epoxy resin of 3,3′,5,5′-tetramethyl-4,4′-biphenol (manufactured by Mitsubishi Chemical Corporation, YX-4000H, epoxy equivalent 196)
E4: Bisphenol A type liquid epoxy resin (manufactured by Nippon Steel Chemical & Materials Co., Ltd., YD-128, epoxy equivalent 186)
E5: Phenol novolac type epoxy resin (manufactured by Nippon Steel Chemical & Materials Co., Ltd., YDPN-638, epoxy equivalent 177)

[Bifunctional phenol compound]
P1: 2,5-di-t-butylhydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent 111)
P2: 4,4'-biphenol (manufactured by Honshu Chemical Industry Co., Ltd., biphenol, hydroxyl equivalent 93)
P3: 3,3',5,5'-tetramethyl-4,4'-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd., hydroxyl equivalent 121)
P4: 3,3'-diphenyl-4,4'-biphenyldiol (manufactured by Sanko Co., Ltd., DOQ-O, hydroxyl equivalent 169)
P5: Bisphenol A (manufactured by Nippon Steel Chemical & Materials Co., Ltd., BPA, hydroxyl equivalent 114)

[catalyst]
C1: tris (2,6-dimethoxyphenyl) phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.)
C2: 49% sodium hydroxide aqueous solution

[Curing agent]
D1: dicyandiamide (manufactured by Nippon Carbide Industry Co., Ltd., dicyandiamide, active hydrogen equivalent 21)

[Curing accelerator]
A1: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., Curesol 2E4MZ)

Example 1

A glass reactor equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction device was charged with 206 parts of E1, 194 parts of P4, and 44 parts of cyclohexanone at room temperature, and while stirring while flowing nitrogen gas, 145 C. and 0.4 part of C1 was added, and the reaction was carried out for 10 hours while maintaining the reaction temperature at 160-170.degree. When the viscosity increased during the reaction, cyclohexanone was added as needed. After completion of the reaction, 156 parts of cyclohexanone including the additional portion and 400 parts of methyl ethyl ketone were diluted and mixed to obtain a phenoxy resin varnish (R1) having a non-volatile content of 40% (solvent ratio: cyclohexanone/methyl ethyl ketone = 1/2). . GPC of the obtained phenoxy resin varnish (R1) is shown in FIG.

The resulting phenoxy resin varnish was applied to a release film (made of polyimide film) with a roller coater so that the thickness after solvent drying was 60 μm, dried at 180° C. for 20 minutes, and then obtained from the release film. The dry film was peeled off. Two of these dried films are stacked and pressed using a vacuum press for 60 minutes under the conditions of a vacuum degree of 0.5 kPa, a drying temperature of 200 ° C., and a press pressure of 2 MPa to obtain a 100 μm thick phenoxy resin film (F1). got A spacer with a thickness of 100 μm was used for thickness adjustment. IR of the obtained phenoxy resin film (F1) is shown in FIG.

Example 2
The procedure of Example 1 is repeated except that 238 parts of E1 and 162 parts of P3 are used instead of 206 parts of E1 and 194 parts of P4, and a phenoxy resin varnish (R2) having a non-volatile content of 40% and a phenoxy A resin film (F2) was obtained.

Example 3
The same procedure as in Example 1 was carried out, except that instead of 206 parts E1 and 194 parts P4, 225 parts E1, 65 parts P1 and 110 parts P4 were used. (R3) and a phenoxy resin film (F3) were obtained.

Example 4
The same operation as in Example 1 was performed except that 173 parts of E1, 44 parts of E2, 43 parts of P2 and 140 parts of P4 were used instead of 206 parts of E1 and 194 parts of P4. % of phenoxy resin varnish (R4) and phenoxy resin film (F4) were obtained.

Example 5
The same procedure as in Example 1 was carried out, except that instead of 206 parts E1 and 194 parts P4, 20 parts E1, 199 parts E3 and 181 parts P4 were used. (R5) and a phenoxy resin film (F5) were obtained.

Example 6
The same procedure as in Example 1 was carried out, except that instead of 206 parts E1 and 194 parts P4, 249 parts E1, 138 parts P1 and 13 parts P2 were used. (R6) and a phenoxy resin film (F6) were obtained.

Comparative example 1
The procedure was as in Example 1, except that 249 parts E3 and 151 parts P3 were used instead of 206 parts E1 and 194 parts P4. However, since the solubility in cyclohexanone after the reaction was poor, 256 parts of cyclohexanone and 300 parts of methyl ethyl ketone were diluted and mixed together with the additional amount to obtain a phenoxy resin varnish (RH1) having a nonvolatile content of 40% (solvent ratio; Cyclohexanone/methyl ethyl ketone=1/1) and a phenoxy resin film (FH1) were obtained.

Comparative example 2
The procedure of Example 1 is repeated except that instead of 206 parts of E1 and 194 parts of P4, 247 parts of E1 and 153 parts of P1 are used. A resin film (FH2) was obtained.

Comparative example 3
The procedure of Example 1 is repeated except that 206 parts of E1 and 194 parts of P4 are replaced by 250 parts of E4 and 150 parts of P5. A resin film (FH3) was obtained.

Example 7
In a glass reaction vessel equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction device, at room temperature, 50 parts of P1, 50 parts of P3, 80 parts of epichlorohydrin (ECH), 40 parts of toluene, n 20 parts of -butyl alcohol and 2 parts of C2 were charged, and the reaction was carried out for 10 hours while maintaining the reaction temperature at 60 to 70°C. When the viscosity increased during the reaction, a mixed solvent (solvent ratio: toluene/n-butyl alcohol=2/1) was added as needed. After completion of the reaction, the mixed solvent was diluted and mixed with 264 parts of the additional portion, 5.5 parts of oxalic acid and 24 parts of pure water were added to neutralize and separate the liquids, and 78 parts of pure water was added twice. After washing with water for liquid separation, the mixture was dehydrated under reflux to obtain a phenoxy resin varnish (R7) having a non-volatile content of 30% (solvent ratio: toluene/n-butyl alcohol=2/1).
Using this phenoxy resin varnish (R7), the same operation as in Example 1 was performed to obtain a phenoxy resin film (F7).

Table 1 summarizes the blending ratios (parts by weight) of Examples 1 to 7 and Comparative Examples 1 to 3. The item "ratio of formula (2)" in the table represents the mol % of the phenylene group represented by formula (2) in all X of the phenoxy resin.

Epoxy equivalent, Mw and solvent solubility were measured using the phenoxy resin varnish, and Tg and thermal conductivity were measured using the phenoxy resin film. Table 2 shows the results.

Example 8
250 parts of the phenoxy resin varnish (R1) obtained in Example 1 (100 parts in solid content), 50 parts of E5, 3.0 parts of D1, 0.2 parts of A1, 40 parts of propylene glycol monomethyl ether , and 40 parts of N,N-dimethylformamide were added and uniformly stirred to obtain a composition varnish.

Further, a glass cloth (WEA 7628 XS13, manufactured by Nitto Boseki Co., Ltd., 0.18 mm thick) was impregnated with the above composition varnish. The impregnated glass cloth was dried in a hot air circulation oven at 150 ° C. for 7 minutes to obtain a prepreg. The obtained 8 sheets of prepreg and copper foil (manufactured by Mitsui Mining & Smelting Co., Ltd., 3EC-III, thickness 35 μm) are stacked on top and bottom, and vacuum pressed at 2 MPa under temperature conditions of 130° C.×15 minutes + 190° C.×80 minutes. to obtain a laminate (B1) having a thickness of 1.6 mm.

Example 9
A laminate (B2) was obtained in the same manner as in Example 8, except that the phenoxy resin varnish (R5) was used instead of the phenoxy resin varnish (R1).

Comparative example 4
A laminate (BH1) was obtained in the same manner as in Example 8, except that the phenoxy resin varnish (RH1) was used instead of the phenoxy resin varnish (R1).

Comparative example 5
A laminate (BH2) was obtained in the same manner as in Example 8, except that the phenoxy resin varnish (RH3) was used instead of the phenoxy resin varnish (R1).

Using the laminate, Tg, thermal conductivity, copper foil peel strength and moisture absorption (water resistance) were measured. Table 3 shows the results.

From the results in Tables 2 and 3, in the examples using the phenoxy resin into which the phenylene group and the biphenylene group were introduced, the thermal conductivity and heat resistance were higher than the phenoxy resin with the biphenylene group alone or the bisphenol group alone, and the solvent solubility was also high. It is possible to reduce the amount of highly soluble high-boiling-point solvent used. As a result, the prepreg drying property in the manufacturing process of the laminate is improved, and the influence of the residual solvent can be suppressed to a low level, so that the heat resistance and the low water absorption are also excellent.

Claims (16)

A phenoxy resin characterized by being represented by the following formula (1) and having a weight average molecular weight of 10,000 to 200,000.

(Here, X is a divalent group, 5 to 95 mol% of X is a phenylene group represented by the following formula (2), Z is independently a hydrogen atom or a glycidyl group, n is a repeating It is the average value of the number, 10 or more and 500 or less.)

(Here, each of R ¹ to R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.)
2. The phenoxy resin according to claim 1, wherein X is a phenylene group represented by formula (2) above and a divalent group represented by formula (3) below.

(Here, each Y is independently an aromatic group, a condensed aromatic group, an alicyclic group, or an alicyclic heterocyclic group, R ⁵ is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or -CO-, -O-, -S-, -SO ₂ -, -C=C-, -C≡C-, -CO-O-, -CO-NH-, -CH=N-, -CH =NN=CH-, -N=N-, -N(O)=N-, and -C(CF ₃ ) ₂ -.) The phenoxy resin according to claim 1 or 2, wherein X is a phenylene group represented by the following formula (4) or a biphenylene group represented by the following formula (5).

(Here, each of R ⁶ and R ⁷ is independently a hydrogen atom, a t-butyl group, or a t-octyl group.)

(Here, each of R ⁸ to R ¹⁵ is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.) Claims 1 to 3, wherein X has both a phenylene group represented by the following formula (6) and/or formula (7) and a biphenylene group represented by the following formula (8) and/or formula (9). The phenoxy resin according to any one of the above.

(In formula (6), t-Bu is a t-butyl group.) Obtained by reacting a bifunctional epoxy resin represented by the following formula (10) with a bifunctional phenol compound represented by the following formula (11), and having a weight average molecular weight of 10,000 to 200,000. A phenoxy resin characterized by:

(Here, both A and B are divalent groups, and 5 to 95 mol% of the total of A and B is a phenylene group represented by the following formula (2). G is a glycidyl group, m is the average number of repetitions, and is 0 or more and 6 or less.)

(Here, each of R ¹ to R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.) 6. The phenoxy resin according to claim 5, wherein A and/or B includes a phenylene group represented by the above formula (2) and a divalent group represented by the following formula (3).

(Here, each Y is independently an aromatic group, a condensed aromatic group, an alicyclic group, or an alicyclic heterocyclic group, R ⁵ is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or -CO-, -O-, -S-, -SO ₂ -, -C=C-, -C≡C-, -CO-O-, -CO-NH-, -CH=N-, -CH =NN=CH-, -N=N-, -N(O)=N-, and -C(CF ₃ ) ₂ -.) A resin composition containing 0.1 to 100 parts by mass of a curing agent as a solid content with respect to 100 parts by mass of the solid content of the phenoxy resin according to any one of claims 1 to 6. A resin composition comprising the phenoxy resin according to any one of claims 1 to 6, an epoxy resin and a curing agent, wherein the solid content ratio of the phenoxy resin to the epoxy resin is 99/1 to 1/99. . 9. The resin composition according to claim 8, which contains 0.1 to 100 parts by mass of a curing agent as a solid content with respect to a total of 100 parts by mass of the solid content of the phenoxy resin and the epoxy resin. Curing agents include acrylic acid ester resins, melanin resins, urea resins, phenolic resins, acid anhydride compounds, amine compounds, imidazole compounds, amide compounds, cationic polymerization initiators, organic phosphines, polyisocyanate compounds, and blocked isocyanates. The resin composition according to any one of claims 7 to 9, which is at least one selected from the group consisting of a compound and an active ester curing agent. 11. The resin composition according to any one of claims 7 to 10, further comprising an inorganic filler. A cured product obtained by curing the resin composition according to any one of claims 9 to 11. A circuit board material obtained from the resin composition according to any one of claims 9 to 11. A laminate for electric/electronic circuits, which is obtained by using the resin composition according to any one of claims 9 to 11. A bifunctional epoxy resin containing a bifunctional epoxy resin represented by the following formula (10) and a bifunctional phenol compound containing a bifunctional phenol compound represented by the following formula (11) are reacted in the presence of a catalyst. A method for producing a phenoxy resin characterized by:

(Here, both A and B are divalent groups, and 5 to 95 mol% of the total of A and B is a phenylene group represented by the following formula (2). G is a glycidyl group, m is the average number of repetitions, and is 0 or more and 6 or less.)

(Here, each of R ¹ to R ⁴ is independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group.) Using a bifunctional phenol compound represented by the following formula (12) and / or formula (13) as a raw material, the ratio of the bifunctional phenol compound having a phenylene group represented by the formula (12) is in the raw material bifunctional phenol compound Production of a phenoxy resin characterized by having a weight-average molecular weight of 10,000 to 200,000, characterized by reacting a raw material bifunctional phenol compound and epihalohydrin in the presence of an alkali. Method.

(Here, R ¹ to R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group, and each Y is independently an aromatic group, a condensed aromatic group, an alicyclic group or an alicyclic heterocyclic group, wherein R ⁵ is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, or -CO-, -O-, -S-, -SO ₂ -, - C=C-, -C≡C-, -CO-O-, -CO-NH-, -CH=N-, -CH=N-N=CH-, -N=N-, -N(O) =N- and a divalent linking group selected from the group consisting of -C(CF ₃ ) ₂ -.)

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