JP7590174B2 - Aromatic ether ether ketone polymer, its method of production, and resin composition and cured resin using said polymer - Google Patents

Description

The present invention relates to a novel polymer containing an aromatic ether ether ketone skeleton, a method for producing the same, a resin composition using the polymer, and a cured resin obtained by curing the same.

Up to now, high molecular weight epoxy resins, such as phenoxy resins, have been used as essential components of epoxy resins used to obtain film- or sheet-shaped epoxy resin cured products. Phenoxy resins with bisphenol A or bisphenol F as the main skeleton have been widely used, but they have problems with heat resistance, low thermal expansion, high thermal conductivity, etc. For example, Patent Document 1 describes an adhesive-attached copper foil using a bisphenol A-type polymer epoxy resin, but the multilayer printed wiring board manufactured by this method has the disadvantage of being inferior in heat resistance and low thermal expansion compared to multilayer printed wiring boards manufactured by conventional techniques. For example, Patent Document 2 discloses a phenoxy resin manufactured from bisphenol A and bisphenol S (4,4'-dihydroxydiphenyl sulfone) as a phenoxy resin with improved heat resistance, but it is still insufficient in terms of heat resistance. Patent Document 3 also discloses an epoxy resin having an ether ether ketone structure, but in the examples, epichlorohydrin is used in an amount 7 to 10 times the amount of phenolic hydroxyl groups, and the synthesis of a polymer is not taught. The disclosed epoxy resin is a low molecular weight substance with a molecular weight of 1000 or less, judging from the epoxy equivalent, and does not have film properties.

Japanese Patent Application Publication No. 7-202418 Japanese Patent Application Publication No. 2-45575 Patent No. 5390491

The object of the present invention is to provide a polymer having excellent heat resistance, low thermal expansion, low moisture absorption, and high toughness, which is suitable for use in preparing a film- or sheet-shaped cured epoxy resin product, a method for producing the polymer, a resin composition using the polymer, and a cured resin product obtained by curing the resin composition.

（式中、Ａは独立に二価の芳香族基を示す。また、ｎは１～５０の数を示す。）で表される芳香族を含むユニットの割合が２０～１００ｗｔ％であり、かつ重量平均分子量が５，０００以上である芳香族エーテルエーテルケトン系重合体である。 The present invention relates to a compound represented by the following general formula (1):

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50) is 20 to 100 wt % of a unit containing an aromatic group, and the weight average molecular weight is 5,000 or more.

（式中、Ａは独立に二価の芳香族基を示す。また、ｎは１～５０の数を示す。）で表されるジグリシジル化合物と、
下記一般式（４）で表されるビスフェノール化合物、ジヒドロキシナフタレン類及び下記一般式（５）で表されるジヒドロキシ化合物からなる群から選択される一種以上とを反応させることを特徴とする芳香族エーテルエーテルケトン系重合体の製造方法。

（式中、ｍは０～２の数を示し、Ｒ₁、Ｒ_２は、独立して、水素原子、炭素数１～８のアルキル基、アリール基、アルコキシ基、アラルキル基又はハロゲン原子を示し、Ｘは直接結合、酸素原子、硫黄原子、－ＳＯ₂－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、－ＣＨ₂－、－ＣＨ（ＣＨ₃）－、－Ｃ（ＣＨ₃）₂－、－φ－又は９，９－フルオレニル基を示す。ここでφはフェニレン基を示す。）

（式中、Ｂは独立に二価の芳香族基を示す。また、ｐは１～５０の数を示す。） The process for producing the aromatic ether ether ketone polymer of the present invention is any one of the following processes.
i) a compound represented by the following general formula (3):

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50),
A method for producing an aromatic ether ether ketone polymer, comprising reacting a bisphenol compound represented by the following general formula (4), a dihydroxynaphthalene, and a dihydroxy compound represented by the following general formula (5),

(In the formula, m is a number from 0 to 2, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group.)

(In the formula, B independently represents a divalent aromatic group, and p represents a number from 1 to 50.)

（式中、ｍは０～２の数を示し、Ｒ₁、Ｒ_２は、独立して、水素原子、炭素数１～８のアルキル基、アリール基、アルコキシ基、アラルキル基又はハロゲン原子を示し、Ｘは直接結合、酸素原子、硫黄原子、－ＳＯ₂－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、－ＣＨ₂－、－ＣＨ（ＣＨ₃）－、－Ｃ（ＣＨ₃）₂－、－φ－又は９，９－フルオレニル基を示す。ここでφはフェニレン基を示す。）で表されるジグリシジル化合物と、下記一般式（７）

（式中、Ａは独立に二価の芳香族基を示す。また、ｎは１～５０の数を示す。）で表されるジヒドロキシ化合物とを反応させることを特徴とする芳香族エーテルエーテルケトン系重合体の製造方法。 ii) a compound represented by the following general formula (6):

(wherein m is a number from 0 to 2, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group), and a diglycidyl compound represented by the following general formula (7):

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50) with a dihydroxy compound represented by the following formula:

iii) A method for producing an aromatic ether ether ketone polymer, comprising reacting a dihydroxy compound represented by the above general formula (7) with epichlorohydrin in the presence of an alkali metal hydroxide.

（式中、ｍは０～２の数を示し、Ｒ₁、Ｒ_２は、独立して、水素原子、炭素数１～８のアルキル基、アリール基、アルコキシ基、アラルキル基又はハロゲン原子を示し、Ｘは直接結合、酸素原子、硫黄原子、－ＳＯ₂－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、－ＣＨ₂－、－ＣＨ（ＣＨ₃）－、－Ｃ（ＣＨ₃）₂－、－φ－又は９，９－フルオレニル基を示す。ここでφはフェニレン基を示す。） In the above polymer and production method, the divalent aromatic groups A and B are each independently an aromatic group represented by the following general formula (2) or a naphthylene group as described below.

(In the formula, m is a number from 0 to 2, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group.)

The present invention also relates to a resin composition containing the aromatic ether ether ketone polymer. The present invention also relates to a cured resin obtained by curing the resin composition.

The polymer of the present invention has crystallinity with a melting point of 100°C or higher, and is expected to have excellent characteristics such as high heat resistance, high thermal conductivity, low thermal expansion, and high toughness, and can be suitably used in fields where it is used as a film- or sheet-shaped epoxy resin cured product, such as multilayer printed wiring boards, adhesives, and coating materials.

The polymer of the present invention has an aromatic-containing unit represented by general formula (1) in a ratio of 20 to 100 weight % (wt%), preferably 30 to 100 wt%, and more preferably 40 to 100 wt%. If the ratio is less than this, the effects of the present invention, high heat resistance, low thermal expansion, and low water absorption, are difficult to achieve. The ratio of the unit represented by general formula (1) that can be contained in the polymer of the present invention can be expressed as the weight ratio of the total amount of the diglycidyl compound represented by general formula (3) and the dihydroxy compound represented by general formula (5) to the total amount of the polymer.

（式中、ｍは０～２の数を示し、Ｒ₁、Ｒ_２は、水素原子、炭素数１～８のアルキル基、アリール基、アルコキシ基、アラルキル基又はハロゲン原子を示し、Ｘは直接結合、酸素原子、硫黄原子、－ＳＯ₂－、－ＣＯ－、－ＣＯＯ－、－ＣＯＮＨ－、－ＣＨ₂－、－ＣＨ（ＣＨ₃）－、－Ｃ（ＣＨ₃）₂－、－φ－、又は９，９－フルオレニル基を示す。ここでφはフェニレン基を示す。）で表される芳香族基であるか、またはナフチレン基である。これらの芳香族基やナフチレン基は、原料となる一般式（４）のビスフェノール化合物や後述のジヒドロキシナフタレン類に由来する。 In the general formula (1), A independently represents a divalent aromatic group. The divalent aromatic group is represented by the following general formula (2):

(wherein m is a number from 0 to 2, _R1 and _R2 each represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group or an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, _-SO2- , -CO-, -COO-, -CONH-, _-CH2- , -CH( _CH3 )-, -C( _CH3 ) _2- , -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group), or a naphthylene group. These aromatic groups and naphthylene groups are derived from the bisphenol compound of general formula (4) that serves as the raw material, or from dihydroxynaphthalenes described below.

In general formula (1), n represents the average number of repeats and is 1 to 50, but preferably 1 to 30. If it is greater than this, the viscosity will increase and the solvent solubility will decrease, making the compound less easy to handle.

（式中、ｍ、Ｒ_１、Ｒ_２、およびＸは上記一般式（４）と同じである。）

Units other than the unit represented by general formula (1) that may be contained in the polymer of the present invention mainly include a unit represented by the following general formula (8) or the following general formula (9), but other units may also be contained.

(In the formula, m, R ₁ , R ₂ , and X are the same as those in the above general formula (4).)

The weight-average molecular weight of the polymer of the present invention is 5,000 or more. If the molecular weight is less than 5,000, when a resin composition using the polymer is applied and dried on a substrate such as copper foil, SUS foil, polyethylene terephthalate film, polyimide film, or glass plate, or when a fiber substrate such as carbon fiber or glass cloth is impregnated and dried, problems such as curling of the substrate or powder falling off during cutting are likely to occur. Furthermore, if the molecular weight exceeds 200,000, even if the polymer is diluted and dissolved in a solvent, the solution viscosity becomes high at a concentration of 40% by weight to 70% by weight that is generally used industrially, making it difficult to apply the polymer to a substrate. Therefore, the weight-average molecular weight of the polymer of the present invention is preferably 5,000 to 100,000, more preferably 10,000 to 60,000.

The reduced viscosity of the polymer of the present invention, measured at 30°C using N-methylpyrrolidone as a solvent, is preferably in the range of 0.2 to 1.2 dL/g, more preferably in the range of 0.3 to 0.8 dL/g. If it is lower than this range, the film properties tend to decrease, and if it is higher than this range, the handling properties tend to decrease.

The polymer of the present invention does not necessarily have to be a two-dimensional polymer as long as it contains the unit of general formula (1). It may have a branched structure or may be a partially three-dimensionally crosslinked polymer. The branched structure or three-dimensional crosslinked structure can be formed by the reaction of the hydroxyl group of general formula (1) with the epoxy group, or by using a trifunctional or higher epoxy resin and a curing agent in combination.

The polymer of the present invention is usually in an amorphous glass state, but may be partially or entirely crystallized. By making it a crystalline polymer, it is possible to expect properties such as heat resistance, high thermal conductivity, low thermal expansion, low moisture absorption, and high toughness based on crystallinity. The degree of crystallization can be grasped by differential scanning calorimetry. Specifically, the peak (endothermic peak) of the endothermic curve accompanying the melting of crystals in differential scanning calorimetry measured at a heating rate of 10°C/min is measured, and the temperature is taken as the melting point, and the heat of fusion is obtained from the integral value of this endothermic peak curve. The preferred heat of fusion of the endothermic peak in differential scanning calorimetry as a crystalline polymer is 5 joules/g (hereinafter referred to as "j/g") or more, preferably 10 j/g or more, and more preferably 20 j/g or more. In addition, the preferred melting point range of the crystalline polymer is one in which the endothermic peak temperature is in the range of 100°C to 350°C when measured at a heating rate of 10°C/min using a differential scanning calorimetry device. If it is lower than this, properties such as heat resistance and low thermal expansion based on crystallinity will decrease, and if it is higher than this, handling will tend to decrease.

Examples of the terminal groups of the polymer of the present invention include epoxy groups, hydroxyl groups, carboxylic acids, amino groups, vinyl groups, mercapto groups, and aromatic groups, with epoxy groups being preferred.

The polymer of the present invention is generally produced by a direct reaction of a dihydric phenol compound with epichlorohydrin in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or by an addition polymerization reaction of a diglycidyl ether compound with a dihydric phenol compound. The polymer of the present invention may be produced by either method, but depending on the structure and molecular weight, there may be problems such as poor solubility in solvents or crystals being precipitated, preventing the molecular weight of the polymer from increasing. Therefore, it is necessary to select the desired polymerization method and polymerization conditions depending on the properties of the desired polymer. Each production method is shown below.

In the case of a direct reaction between a dihydric phenol compound and epichlorohydrin, a dihydroxy compound represented by general formula (7) is used as the dihydric phenol compound, and it is preferable that the proportion of the dihydroxy compound of general formula (7) is 10 mol% or more of the total dihydric phenol compounds used. At 10 mol% or more, the effect of introducing the ether ether ketone skeleton is sufficient, and a cured product having heat resistance, low thermal expansion, low moisture absorption, and high toughness is obtained, which is preferable.

The amount of epichlorohydrin used in the reaction between a dihydric phenol compound and epichlorohydrin is usually 1 to 5 moles per mole of hydroxyl groups in the dihydric phenol compound, but is preferably in the range of 1 to 3 moles. By varying the amount within this range, the molecular weight of the polymer can be adjusted. This reaction is usually carried out at a temperature of 120°C or less.

In this reaction, a quaternary ammonium salt or a polar solvent such as dimethyl sulfoxide or diglyme may be used. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetrabutylammonium chloride, and benzyltriethylammonium chloride. The amount of the quaternary ammonium salt added is preferably in the range of 0.1 to 2.0 wt% relative to the dihydric phenol compound. This range is preferable in terms of the effect of adding the quaternary ammonium salt and the amount of hardly hydrolyzable chlorine produced. The amount of the polar solvent added is preferably in the range of 10 to 200 wt% relative to the dihydric phenol compound. This is for the effect of the addition and to optimize the reactivity and yield due to volumetric efficiency. After the reaction is completed, the excess epichlorohydrin and the solvent are distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, and washed with water to remove inorganic salts and remaining solvents, and then the solvent is distilled off to obtain an epoxy resin. More advantageously, the obtained epoxy resin is further added with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in an amount 1 to 30 times the amount of the remaining hydrolyzable chlorine, and a ring-closing reaction is carried out. The temperature of this ring-closing reaction is usually 100°C or less, preferably 90°C or less.

On the other hand, in the case of a method using an addition polymerization reaction between a diglycidyl ether compound and a dihydric phenol compound, the following i) and ii) can be mentioned. First, i) is a method in which a bisphenol compound represented by general formula (4), a dihydroxynaphthalene, and/or a dihydroxy compound represented by general formula (5) is used as a dihydric phenol compound, and these are reacted with a diglycidyl ether compound represented by general formula (3). On the other hand, ii) is a method in which a diglycidyl ether compound represented by general formula (6) is reacted with a dihydroxy compound represented by general formula (7) as a dihydric phenol compound.

In general formulas (4) and (6), R ₁ and R ₂ independently represent a substituent selected from a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group, or a halogen atom, and are preferably a hydrogen atom or a methyl group. The linking positions of the benzene ring include the 1,4-position, the 1,3-position, and the 1,2-position, and the 1,4-position is particularly preferred. This is because the 1,3-position and the 1,2-position cannot be expected to improve physical properties such as heat resistance, low thermal expansion, and high toughness, as compared with the 1,4-position.

Preferable examples of the bisphenol compound represented by the general formula (4) include hydroquinone, resorcinol, bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 1,4-bis(4-hydroxyphenoxy)benzene, 1,3-bis(4-hydroxyphenoxy)benzene, 4,4'-bis(4-hydroxyphenoxy)diphenyl ether, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfide, and bisphenol fluorene.
Examples of the dihydroxynaphthalenes include 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, and 2,7-naphthalenediol. These bisphenol compounds and dihydroxynaphthalenes can be used as a mixture with a dihydroxy compound represented by the general formula (5) described below.

The dihydroxy compound represented by the general formula (5) or (7) can be synthesized, for example, by reacting a benzophenone halide such as 4,4'-difluorobenzophenone with a bisphenol compound represented by the general formula (4) or a dihydroxynaphthalene in the presence of a basic compound, but is not limited thereto. The A and B units in the general formulas (5) and (7) are divalent aromatic groups derived from the bisphenol compound or dihydroxynaphthalene thus reacted, respectively, and are preferably the aromatic group represented by the general formula (2) or a naphthylene group as described above.

The diglycidyl compounds represented by general formula (3) or general formula (6) are generally obtained by directly reacting the bisphenol compound represented by general formula (4) or the dihydroxy compound represented by general formula (7) with epichlorohydrin, and normal reaction conditions can be used.

The reaction by addition polymerization between such a diglycidyl ether compound and a dihydric phenol compound can be carried out in the presence of a catalyst such as an amine, imidazole, triphenylphosphine, or phosphonium salt. The molar ratio of the diglycidyl ether compound to the dihydric phenol compound is usually in the range of 3:1 to 1:3, preferably 2:1 to 1:2, and more preferably 1.1:1 to 1:1.1. The closer the molar ratio of the diglycidyl ether compound to the dihydric phenol compound is to 1, the higher the molecular weight of the resulting polymer will be. Other conditions for the addition polymerization reaction can be the usual general reaction conditions.

This reaction can be carried out without a solvent, but if the reaction is carried out without a solvent, branching reactions are likely to occur and, in some cases, gelation may occur. Therefore, it is preferable to use a solvent in this reaction. Examples of solvents include aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; aromatics such as benzene, toluene, ortho-xylene, meta-xylene, para-xylene, chlorobenzene, and dichlorobenzene; aliphatic amides such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; and dimethyl sulfoxide. Two or more of these organic solvents may be selected and used as a mixed solvent.

In this polymerization reaction, the diglycidyl ether compound and the dihydric phenol compound can each be used as a mixture of two or more types, but the diglycidyl ether compound and the dihydric phenol compound must be selected so that the aromatic unit represented by general formula (1) is 20 to 100 wt % in the obtained polymer. If it is less than 20 wt %, the effect of introducing the ether ether ketone structure is insufficient, and a cured product with heat resistance, low thermal expansion, and toughness cannot be obtained, which is not preferable.

When the resin composition of the present invention uses a polymer having a weight average molecular weight of 5,000 or more, the resin flow during molding is small and the circuit embedding ability is often somewhat insufficient. In this case, in order to ensure sufficient circuit embedding ability, another low molecular weight epoxy resin can be added. In this case, the molecular weight of the low molecular weight epoxy resin is 3,000 or less, preferably 1,500 or less, and more preferably 800 or less, in weight average molecular weight.

In this case, the blending ratio of the polymer of the present invention to the low molecular weight epoxy resin is preferably 10 to 90 parts by weight, more preferably 20 to 60 parts by weight, of the low molecular weight epoxy resin per 100 parts by weight of the polymer of the present invention. If it is less than this, the improvement in the flowability of the resin during molding is small, and if it is more than this, the heat resistance and moisture resistance of the cured product may decrease.

As a low molecular weight epoxy resin, in order to provide circuit embedding properties without compromising physical properties such as flexibility and heat resistance after curing, it is preferable to use an aromatic epoxy resin with an epoxy equivalent of 100 g/eq to 2,000 g/eq. If the epoxy equivalent exceeds 2,000 g/eq, the effect of improving circuit embedding properties is not sufficient, and the crosslink density is likely to be low, making it difficult to obtain a heat-resistant cured film. In addition, with an aliphatic epoxy resin, even if circuit embedding properties are obtained, heat resistance is insufficient. In addition, if the epoxy equivalent is less than 100 g/eq, the crosslink density of the cured product becomes high, which increases the shrinkage rate of the cured product, and the deformation of the cured product tends to increase, as well as the water absorption rate. For these reasons, the epoxy equivalent of the low molecular weight epoxy resin is preferably 130 g/eq to 1,500 g/eq, more preferably 150 g/eq to 1,000 g/eq. Preferred low molecular weight epoxy resins include epoxy resins obtained by reacting a bisphenol compound represented by the above general formula (4) with epichlorohydrin, such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, tetramethylbisphenol F type epoxy resins, tetrabromobisphenol A type epoxy resins, etc., but are not limited to these. These epoxy resins may be used alone or in combination of two or more types.

In addition, in the present invention, other high molecular weight epoxy resins can be added to improve film properties.

In this case, the weight blending ratio of the polymer of the present invention to the high molecular weight epoxy resin is preferably in the range of 10 to 90 parts by weight, more preferably 20 to 60 parts by weight, of the high molecular weight epoxy resin per 100 parts by weight of the total amount of the polymer of the present invention and the high molecular weight epoxy resin. If it is less than this, the degree of improvement in the film properties of the cured product is small, and if it is more than this, the heat resistance and low thermal expansion properties of the cured product may decrease.

The preferred molecular weight of the high molecular weight epoxy resin is a weight average molecular weight of 5,000 to 100,000, more preferably 10,000 to 60,000. Examples of the high molecular weight epoxy resin include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, and tetrabromobisphenol A type epoxy resin.

The resin composition of the present invention advantageously contains an epoxy resin, a phenoxy resin, or a compound containing an epoxy group. Such a resin can be a polymer of the present invention. When the resin composition of the present invention contains an epoxy resin or a compound containing an epoxy group, it is desirable to use a curing agent.

As the hardener, all commonly known hardeners can be used. For example, dicyandiamide and its derivatives, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole and their derivatives, divalent phenol compounds such as bisphenol A, bisphenol F, brominated bisphenol A, naphthalenediol, and dihydroxybiphenyl, novolac-type phenolic resins obtained by condensation reactions of phenols such as phenol, cresol, bisphenol A, naphthol, and naphthalenediol with aldehydes such as formaldehyde or ketones, and phenols such as phenol, cresol, bisphenol A, naphthol, and naphthalenediol with hydroxyl groups. Examples of commonly used epoxy resin curing agents include, but are not limited to, phenolic compounds such as aralkyl phenolic resins obtained by condensation reaction with rylene glycols, acid anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and hexahydrophthalic anhydride, amine compounds such as polyamidoamines obtained by condensation reaction between acids such as diaminodiphenylmethane, triethylenetetramine, isophoronediamine, and dimer acid and polyamines, and hydrazides such as adipic acid dihydrazide and isophthalic acid dihydrazide. These curing agents may be used alone or in combination of two or more.

In the resin composition of the present invention, preferably the epoxy resin composition, a solvent may be used to maintain an appropriate viscosity when applied to a substrate. The viscosity adjusting solvent is one that does not remain in the epoxy resin composition when the solvent is dried at 80°C to 200°C, and specific examples include, but are not limited to, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, dioxane, ethanol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, cyclohexanone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, etc. These solvents may be used alone or in combination of two or more types.

The resin composition of the present invention may contain silica, calcium carbonate, talc, aluminum hydroxide, mica, alumina, aluminum nitride, etc. to impart heat resistance and flame retardancy, reduce the thermal expansion coefficient, increase the thermal conductivity, etc., and may also contain epoxy silane coupling agents and rubber components to improve adhesion, to the extent that the properties of the cured product of the resin composition are not adversely affected.

If necessary, a curing accelerator may be used in the resin composition of the present invention. For example, various known curing accelerators such as amine-based, imidazole-based, triphenylphosphine, and phosphonium salt-based accelerators can be used, but the invention is not limited to these. When a curing accelerator is used, the amount is preferably in the range of 0.01 wt% to 10 wt% of the resin component. If the amount exceeds 10 wt%, there is a concern that storage stability may deteriorate, and this is not preferred.

When the resin composition of the present invention is an epoxy resin composition, for example, the viscosity is adjusted to 15 Pa·s or less, preferably 10 Pa·s or less, using the solvent mentioned above, an appropriate amount of curing agent is added so as to have a certain curing time, and a curing accelerator is optionally added to make a varnish, which is then applied to a substrate and the solvent is volatilized at 100°C to 160°C to form a prepreg, which can then be cured by heating to form a cured product.

The present invention will be specifically described below based on the embodiments of the invention.

The present invention will be explained in more detail below with reference to the following examples. In the examples, the molecular weight and physical properties were measured by preparing samples and carrying out the measurements according to the methods described below. Unless otherwise specified, "parts" refers to "parts by weight."

1) Molecular weight of dihydroxy resin and epoxy resin Measurements were performed using a GPC measurement device (515A GPC, manufactured by Nippon Waters Co., Ltd.) and three TSKgel G2000HXL (manufactured by Tosoh Corporation) and one TSKgel G4000HXL (manufactured by Tosoh Corporation) columns, with an RI detector, tetrahydrofuran as the solvent, a flow rate of 1.0 ml/min, and a column temperature of 38° C.

2) Melt Viscosity The melt viscosity was measured at 150° C. to 190° C. using a CAP2000H rotational viscometer manufactured by BROOKFIELD.

3) Softening point: Determined in accordance with JIS K 7234 at a temperature rise rate of 5° C./min.

4) Measurement of hydroxyl group equivalent Using a potentiometric titrator, acetylation was carried out with 1.5 mol/L acetyl chloride in 1,4-dioxane as a solvent, and the excess acetyl chloride was decomposed with water and titrated with 0.5 mol/L potassium hydroxide.

5) Measurement of epoxy equivalent: Using a potentiometric titrator, methyl ethyl ketone was used as a solvent, a tetraethylammonium bromide acetate solution was added, and the measurement was carried out using a 0.1 mol/L perchloric acid-acetic acid solution in the potentiometric titrator.

6) Thermal decomposition temperature and carbon residue ratio Using a Hitachi High-Tech Science TG/DTA7300 differential thermal thermogravimetry device, the temperature was increased at a rate of 10°C/min under a nitrogen stream. The temperature at 5 wt% weight loss (T-5%), the temperature at 10 wt% weight loss (T-10%), and the carbon residue ratio at 700°C were determined.

7) Linear expansion coefficient, glass transition point (Tg)
The measurements were performed using a Hitachi High-Tech Science TMA7100 thermomechanical analyzer at a temperature rise rate of 10° C./min.

8) Water Absorption Rate The water absorption rate was determined as the weight change rate after absorbing moisture for 100 hours under conditions of 85° C. and a relative humidity of 85%.

9) Hydrolyzable chlorine: 0.5 g of a sample was dissolved in 30 ml of dioxane, 10 ml of 1N KOH was added, and the mixture was boiled under reflux for 30 minutes. The mixture was then cooled to room temperature, and 100 ml of 80% acetone water was added. The content of the solution was measured by potentiometric titration with a 0.002N AgNO3 aqueous solution.

Reference Example 1
A 2L separable flask was charged with 110g (1.0 mol) of resorcinol, 109g (1.0 mol) of 4,4'-difluorobenzophenone (DFBP), 276g of anhydrous potassium carbonate, 1200g of N-methylpyrrolidone (NMP), and 200g of toluene, and the mixture was reacted for 4 hours under a nitrogen stream while heating to 140°C and distilling off water. The mixture was then heated to 160°C and reacted for 4 hours under reduced pressure while distilling off NMP. The mixture was cooled to room temperature, dissolved in 1400g of methyl isobutyl ketone (MIBK), neutralized with a 30% aqueous sulfuric acid solution, and washed with water. The MIBK was then removed under reduced pressure, and the mixture was further reacted at 210°C for 4 hours. The remaining resorcinol was removed under reduced pressure to obtain 111g of a resinous solid (dihydroxy resin A). The softening point was 132° C., the melt viscosity at 180° C. was 3.3 Pa·s, and the hydroxyl (OH) equivalent was 468 g/eq. GPC measurement revealed that the component ratio of the product was 10.3% for p=1 in general formula (5), 13.5% for p=2, 14.5% for p=3, 12.2% for p=4, 9.5% for p=5, 7.2% for p=6, 28.2% for p≧7, and 4.6% for others.

Reference Example 2
A 0.5L separable flask was charged with 30g of dihydroxy resin A, 59g of epichlorohydrin (ECH), and 9g of diethylene glycol dimethyl ether, and 5.3g of 48.8% aqueous sodium hydroxide solution was added dropwise at 62°C under reduced pressure over 3 hours. During this time, the water produced was removed from the system by azeotropy with ECH, and the distilled ECH was returned to the system. After the dropwise addition was completed, the reaction was continued for another 1 hour to dehydrate. Then, the ECH was removed under reduced pressure, 80g of toluene was added to it to dissolve it, the salt produced was removed by filtration, and further washing with water was performed. 1.8g of 48.8% aqueous potassium hydroxide solution was added to it, and the reaction was performed at 80°C for 2 hours. Then, after washing with water, the toluene was removed under reduced pressure to obtain 23.1g of a resinous material (epoxy resin A). The softening point was 94°C, and the melt viscosity at 150°C was 3.6 Pa·s. The hydrolyzable chlorine content was 0.3%, and the epoxy equivalent was 422 g/eq.

Reference Example 3
109g (0.5mol) of DFBP, 200g (1.0mol) of 4,4'-dihydroxydiphenylmethane, 123g of anhydrous potassium carbonate, 1120g of NMP, and 120g of toluene were charged into a 2L separable flask and stirred at room temperature for 1 hour under a nitrogen stream. Then, the temperature was raised to 140°C and stirred for 4 hours while distilling off water. Then, the temperature was further raised to 205°C and stirred for 4 hours while distilling off NMP. Then, the mixture was returned to room temperature, slowly poured into 1500mL of water while stirring, dispersed, washed with water, filtered, and further poured into 1500mL of water and neutralized with a 30% aqueous sulfuric acid solution, then washed with water, filtered, and dried to obtain 232g of a milky white solid product (dihydroxy resin B). The OH equivalent was 457g/eq. From the GPC measurement, the component ratio of the product was 39.1% for p=1 in the general formula (5), 32.2% for p=2, 15.9% for p=3, 6.0% for p=4, 4.4% for p≧5, and 2.4% for others.

Reference Example 4
50.0g of the dihydroxy resin B obtained in Reference Example 3, 185g of ECH, and 500g of NMP were charged and dissolved at 65°C, and then 9.1g of 48.8% aqueous sodium hydroxide solution was dropped and reacted for 4 hours. Then, ECH and the generated water were distilled off at 85°C under reduced pressure, and the generated salt was removed by filtration. Then, the reaction liquid was dropped into 2000mL of water while stirring to precipitate the product. Then, after repeated washing with water, it was dried to obtain 50.8g of a white solid (epoxy resin B). The melt viscosity at 190°C was 0.1 Pa·s, and the epoxy equivalent was 579g/eq.

Reference Example 5
A 2L separable flask was charged with 60g (0.28mol) of DFBP, 176.2g (1.10mol) of 1,6-dihydroxynaphthalene, 152g of anhydrous potassium carbonate, 1000g of NMP, and 150g of toluene, and stirred at room temperature for one hour under a nitrogen stream. The mixture was then heated to 140°C and stirred for four hours while distilling off water. The mixture was then further heated to 160°C and stirred for four hours under reduced pressure while distilling off NMP. The mixture was then returned to room temperature, and 1000g of MIBK was added and dissolved, neutralized with a 30% aqueous sulfuric acid solution, and repeatedly washed with water. MIBK was then removed from the MIBK layer under reduced pressure, and 196g of a resinous solid (dihydroxy resin C) was obtained. The softening point was 44°C, the melt viscosity at 150°C was 85mPa·s, and the OH equivalent was 212g/eq. From the GPC measurement, the component ratio of the product was 35.1% unreacted 1,6-naphthalenediol, 30.0% of p=1 in the general formula (5), 17.7% of p=2, 8.5% of p=3, 3.9% of p=4, 2.4% of p≧5, and 2.3% of others.

Example 1
In a 500 ml glass separable flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet, 20 parts of bisphenol A type epoxy resin (epoxy resin D; manufactured by Nippon Steel Chemical & Material Co., Ltd., YD-8125, epoxy equivalent 173 g/eq.), 54.1 parts of dihydroxy resin A synthesized in Reference Example 1, and 200 parts of NMP were weighed out and heated to 110° C. with stirring under a nitrogen stream to dissolve uniformly, and then 0.2 parts of 2-ethyl-4-methylimidazole was added as a catalyst and reacted at 150° C. for 5 hours to obtain a polymer solution. The obtained polymer solution was dropped into a large amount of methanol, and 72 g of a precipitated white polymer (polymer A) was recovered. The reduced viscosity of the obtained polymer measured at 30° C. using NMP as a solvent was 0.43 dL/g. The proportion of the unit represented by the general formula (1) was 73 wt %. The weight average molecular weight was 38,000.

Example 2
Using 52.8 parts of dihydroxy resin B instead of dihydroxy resin A, the reaction was carried out in the same manner as in Example 1 to obtain 71 parts of a polymer (Polymer B). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.52 dL/g. The proportion of the unit represented by general formula (1) was 72 wt%. The weight average molecular weight was 47,000.

Example 3
The reaction was carried out in the same manner as in Example 1, except that 24.5 parts of dihydroxy resin C was used instead of dihydroxy resin A, to obtain 43 parts of polymer (Polymer C). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.38 dL/g. The proportion of the unit represented by general formula (1) was 55 wt%. The weight average molecular weight was 28,000.

Example 4
Using 20 parts of epoxy resin A and 22.2 parts of dihydroxy resin A, a reaction was carried out in the same manner as in Example 1 to obtain 41 parts of polymer (Polymer D). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.41 dL/g. The proportion of the unit represented by general formula (1) was 100 wt%. The weight average molecular weight was 36,000.

Example 5
Using 40 parts of epoxy resin B and 7.9 parts of bisphenol A (dihydroxy resin D), a reaction was carried out in the same manner as in Example 1 to obtain 45 parts of a polymer (polymer E). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.48 dL/g. The proportion of the unit represented by general formula (1) was 83 wt%. The weight average molecular weight was 46,000.

Example 6
Using 20 parts of a biphenyl-based epoxy resin (epoxy resin E; YX-4000H, manufactured by Mitsubishi Chemical, epoxy equivalent: 193 g/eq.) and 22 parts of dihydroxy resin C, a reaction was carried out in the same manner as in Example 1 to obtain 40 parts of a polymer (polymer F). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.36 dL/g. The proportion of the unit represented by general formula (1) was 52 wt%. The weight average molecular weight was 27,000.

Comparative Example 1
Using 30 parts of epoxy resin D and 19.8 parts of dihydroxy resin D, a reaction was carried out in the same manner as in Example 1 to obtain 47 parts of a polymer (Polymer G). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.56 dL/g. The proportion of the unit represented by general formula (1) was 0 wt%. The weight average molecular weight was 57,000.

Comparative Example 2
Using 30 parts of epoxy resin E and 17.7 parts of dihydroxy resin D, a reaction was carried out in the same manner as in Example 1 to obtain 46 parts of a polymer (Polymer H). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.53 dL/g. The proportion of the unit represented by general formula (1) was 0 wt%. The weight average molecular weight was 53,000.

Comparative Example 3
Using 40 parts of epoxy resin D, 8.1 parts of dihydroxy resin A, and 24.3 parts of dihydroxy resin D, the reaction was carried out in the same manner as in Example 1 to obtain 68 parts of a polymer (Polymer I). The reduced viscosity of the obtained polymer at 30°C using NMP as a solvent was 0.51 dL/g. The proportion of the unit represented by general formula (1) was 11.2 wt%. The weight average molecular weight was 51,000.

Examples 7 to 12, Comparative Examples 4 to 6
Test pieces were prepared by press molding using the polymers obtained in Examples 1 to 6 and Comparative Examples 1 to 3, and were subjected to evaluation of various physical properties. The results are shown in Table 1.

Claims (8)

The following general formula (1)

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50) is 30 to 100 wt % of a unit containing an aromatic group, and the weight average molecular weight is 27,000 or more. The divalent aromatic group A is represented by the following general formula (2):

The aromatic ether ketone polymer according to claim 1, which is an aromatic group represented by the formula (wherein m is a number from 0 to 2, _R1 and _R2 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, _-SO2- , -CO-, -COO-, -CONH-, _-CH2- , -CH( _CH3 )-, -C( _CH3 ) _2- , -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group), or a naphthylene group. The following general formula (1)

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50) is 20 to 100 wt % of a unit containing an aromatic group, and the weight average molecular weight is 5,000 or more ,
The following general formula (3)

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50),
A method for producing an aromatic ether ether ketone polymer, comprising reacting a bisphenol compound represented by the following general formula (4), a dihydroxynaphthalene, and a dihydroxy compound represented by the following general formula (5),

(In the formula, m is a number from 0 to 2, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group.)

(In the formula, B independently represents a divalent aromatic group, and p represents a number from 1 to 50.) A method for producing the aromatic ether ether ketone polymer according to claim 1 or 2, comprising the steps of:
The following general formula (6)

(wherein m is a number from 0 to 2, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group), and a diglycidyl compound represented by the following general formula (7):

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50) with a dihydroxy compound represented by the following formula: The following general formula (1)

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50) is 20 to 100 wt % of a unit containing an aromatic group, and the weight average molecular weight is 5,000 or more ,
The following general formula (7)

(wherein A independently represents a divalent aromatic group, and n represents a number from 1 to 50) with epichlorohydrin in the presence of an alkali metal hydroxide. The divalent aromatic groups A and B are independently represented by the following general formula (2):

A method for producing an aromatic ether ether ketone polymer described in any one of claims 3 to 5, wherein the aromatic group represented by the formula (wherein m is a number from 0 to 2, R ₁ and R ₂ independently represent a hydrogen atom, an _alkyl group having 1 to 8 carbon atoms, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, and X represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ -, -CH(CH _{3 )-, -C(CH 3 )} 2 -, -φ- or a 9,9-fluorenyl group, where φ represents a phenylene group), or a naphthylene group. A resin composition comprising the aromatic ether ether ketone polymer according to claim 1 or 2. A cured resin obtained by curing the resin composition according to claim 7.