JP2021113293A - Aromatic ketone-type polymer and method for producing the same, and resin composition and resin molding containing aromatic ketone-type polymer - Google Patents

Abstract

To provide a polymer suitably used for the preparation of a film-like or sheet-like epoxy resin composition or epoxy resin cured product that features high heat resistance, high thermoconductivity, low thermal expandability and high toughness.SOLUTION: An aromatic ketone-type polymer has a unit represented by general formula (1) (where R1, R2 independently represent a hydrogen atom, a C1-8 alkyl group, an aryl group, an alkoxy group, an aralkyl group or a halogen atom, n is a number selected from 1-3), the proportion of the unit being 10-100 mol%. The aromatic ketone-type polymer has a weight average molecular weight of 5,000 or more and has crystallinity. There is also provided a method for producing the same.SELECTED DRAWING: None

Description

The present invention relates to a novel polymer containing an aromatic ketone skeleton, a method for producing the same, a resin composition using this polymer, and a resin molded product obtained by molding the polymer.

So far, as an epoxy resin used for obtaining a film-shaped or sheet-shaped epoxy resin molded product, a high-molecular-weight epoxy resin typified by a phenoxy resin has been used as an essential component. As the phenoxy resin, those having bisphenol A or bisphenol F as the main skeleton have been widely used, but there are problems in heat resistance, low thermal expansion, high thermal conductivity and the like. For example, Patent Document 1 describes a copper foil with an adhesive using a bisphenol A type polymer epoxy resin, but a multilayer printed wiring board manufactured by this method is a multilayer printed wiring board manufactured by a conventional technique. Compared to a printed wiring board, it has a drawback that it is inferior in heat resistance and low thermal expansion because it has a low glass transition point. Further, for example, Patent Document 2 describes a phenoxy produced from bisphenol A and bisphenol S (4,4'-dihydroxydiphenylsulfone) in order to provide a self-bonding insulated wire having excellent thermal adhesiveness and heat-resistant deformation. The resin is disclosed. However, this has a higher viscosity than a phenoxy resin having the same molecular weight, has a problem in handling as a single resin, and is still insufficient in terms of heat resistance. Furthermore, the phenoxy resin is hardly soluble in general solvents such as toluene and methyl ethyl ketone, and has a drawback in handleability. Further, most of the phenoxy resins known so far are amorphous solids having no crystallinity, and there is a problem that the physical properties are significantly deteriorated above the glass transition point. Further, Patent Document 3 discloses an epoxy resin having a benzophenone structure, but it is a low molecular weight body having a number average molecular weight of 330 to 5000 and does not have film properties.

Patent Document 4 discloses a carbon fiber composite material using polyphenylene sulfide as an improved heat resistance, but it requires a high molding temperature of 300 ° C. or higher and has a high viscosity, so that it is resin-impregnable. Was inferior.

Further, although Non-Patent Document 1 discloses a polymer having a DHBP structure having a benzophenone skeleton, it is only disclosed as a thermoplastic resin having Tg instead of a crystal structure. By the way, when the epoxy resin reacts with the phenol compound, the epoxy group is opened to generate a secondary hydroxyl group, but depending on the conditions, the generated secondary hydroxyl group also reacts with the epoxy group to form a branched structure. This reaction can occur when the reaction temperature is high, the reaction is carried out in a solvent-free and highly viscous state, or when stirring is insufficient. The branched structure hinders the packing of molecules, inhibits crystallization, and gives an amorphous solid that does not crystallize. Although the reaction conditions are not described in Non-Patent Document 1, it is presumed that the reaction conditions under which a branched structure can occur were taken because the crystallinity was not confirmed. That is, the high molecular weight compound of the epoxy resin having a specific benzophenone skeleton is crystalline by suppressing the reaction between the generated secondary hydroxyl group and the epoxy group by lowering the viscosity and the reaction temperature using a solvent. It is different from the present invention in which the above is found.

Japanese Unexamined Patent Publication No. 7-202418 Japanese Unexamined Patent Publication No. 2-45575 Japanese Unexamined Patent Publication No. 9-227654 JP-A-2019-172878

H.Van Hoorn, A Dynamic Mechanical Study of the Effect of Chemical Variations on the Internal Mobility of Linear Epoxy Resins (Polyhydroxyethers), Journal of applied polymer science, Volume 12, No.4, April 1968, p.871-888

An object of the present invention is heat resistance, high thermal conductivity, and low thermal expansion, which are suitably used for preparing resin compositions for fiber-reinforced composite materials such as film-shaped or sheet-shaped cured epoxy resin products, glass fibers, and carbon fibers. An object of the present invention is to provide a polymer having excellent properties, low moisture absorption, and high toughness, a method for producing the same, a resin composition using this polymer, and a resin molded product obtained by molding the resin composition.

（式中、Ｒ₁、Ｒ₂は、それぞれ独立して、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、ｎは１〜３の数を示す。）で表されるユニットの割合が１０〜１００モル％であり、かつ重量平均分子量が５，０００以上であるとともに、結晶性を有する芳香族ケトン型重合体である。 The present invention has the following general formula (1),

(In the formula, 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 n is a number of 1 to 3 It is an aromatic ketone type polymer having a ratio of units represented by (shown) of 10 to 100 mol%, a weight average molecular weight of 5,000 or more, and crystallinity.

Further, it is desirable that the aromatic ketone type polymer satisfies any one or more of the following a) to c).
a) In the general formula (1), the benzene ring has a 1,4-phenylene structure, R ₁ and R ₂ are both hydrogen atoms, and n is 1.
b) The peak temperature of the endothermic curve associated with melting of the crystal in the differential scanning calorimetry measured at a heating rate of 10 ° C./min shall be in the range of 100 ° C. to 350 ° C.
c) The integral value of the peak curve of the endothermic curve associated with melting of the crystal in the differential scanning calorimetry measured at a heating rate of 10 ° C./min shall be 10 joules / g or more.

Further, the present invention is a resin composition characterized by containing the above aromatic ketone type polymer. Further, the present invention is a resin molded product obtained by curing the above resin composition.

（式中、Ｒ₁、Ｒ₂は、それぞれ独立して、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、ｎは１〜３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（３）、

〔式中、ｍは０〜３の数を示し、Ｒ_３、Ｒ_４は、それぞれ独立して、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、それぞれ独立して、直接結合、酸素原子、硫黄原子、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−ＣＨ＝Ｎ−、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ₃）−、−ＣＨ₂−、−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−、−φ−、−ＣＨ₂−φ−ＣＨ₂−、−ＣＨ（ＣＨ₃）−φ−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−φ−Ｃ（ＣＨ₃）₂−、−ＣＨ₂−φ−φ−ＣＨ₂−、−ＣＨ（ＣＨ₃）−φ−φ−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−φ−φ−Ｃ（ＣＨ₃）₂−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。〕で表されるビスフェノール化合物とを反応させることを特徴とする製造方法。 The method for producing the aromatic ketone type polymer of the present invention is any of the following i) to iii).
i) The following general formula (2),

(In the formula, 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 n is a number of 1 to 3 The diglycidyl compound represented by (shown) and the following general formula (3),

[In the formula, m represents a number from 0 to ₃ , and R 3 and R ₄ independently form 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. Indicated, X is an independent direct bond, oxygen atom, sulfur atom, -SO-, -SO _2- , -CO-, -COO-, -CONH-, -CH = N-, -CH = CH. −, −CH = C (CH ₃ ) −, −CH ₂ −, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, _{−φ−, −CH 2} −φ−CH ₂ −, −CH (CH ₃ ) −φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−C (CH ₃ ) ₂ −, −CH ₂ −φ−φ−CH ₂ −, −CH (CH ₃ ) −φ−φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−φ−C (CH ₃ ) ₂ -or 9,9-fluorenyl group. Here, φ indicates a phenylene group. ], A production method characterized by reacting with a bisphenol compound represented by.

〔式中、ｍ、Ｒ_３、Ｒ_４及びＸは、一般式（３）と同じである。〕で表されるジグリシジル化合物と、下記一般式（５）、

〔式中、Ｒ₁、Ｒ₂及びｎは、一般式（２）と同じである。〕で表されるビスフェノール化合物とを反応させることを特徴とする製造方法。 ii) The following general formula (4),

[In the formula, m, R ₃ , R ₄ and X are the same as the general formula (3). ], And the following general formula (5),

[In the formula, R ₁ , R ₂ and n are the same as the general formula (2). ], A production method characterized by reacting with a bisphenol compound represented by.

iii) A production method characterized by reacting a bisphenol compound represented by the above general formula (5) with epichlorohydrin in the presence of an alkali metal hydroxide.

The polymer of the present invention has crystallinity having a melting point of 100 ° C. or higher, and is expected to have excellent features of high heat resistance, high thermal conductivity, low thermal expansion and high toughness. It can be suitably used in the field of being used as a film-like or sheet-like epoxy resin cured product such as a fiber-reinforced composite material such as an adhesive or a coating material.

FIG. 1 shows a DSC chart of the polymer A according to Example 1. FIG. 2 shows an infrared absorption spectrum of the polymer A according to Example 1. FIG. 3 shows a DSC chart of the polymer B according to Example 2.

Hereinafter, the present invention will be described in detail.

The polymer of the present invention contains a unit represented by the above general formula (1), and the proportion thereof is 10 to 100 mol%, preferably 40 to 100 mol%, more preferably 60. It is in the range of ~ 100 mol%. If it is less than this, it is difficult to exhibit the effects of the present invention, such as high heat resistance, low thermal expansion, and high thermal conductivity.

〔式中、ｍは０〜３の数を表し、Ｒ_３、Ｒ_４は、それぞれ独立して、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、それぞれ独立して、直接結合、酸素原子、硫黄原子、−ＳＯ−、−ＳＯ₂−、−ＣＯ−、−ＣＯＯ−、−ＣＯＮＨ−、−ＣＨ＝Ｎ−、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ₃）−、−ＣＨ₂−、−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−、−φ−、−ＣＨ₂−φ−ＣＨ₂−、−ＣＨ（ＣＨ₃）−φ−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−φ−Ｃ（ＣＨ₃）₂−、−ＣＨ₂−φ−φ−ＣＨ₂−、−ＣＨ（ＣＨ₃）−φ−φ−ＣＨ（ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−φ−φ−Ｃ（ＣＨ₃）₂−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。〕 Examples of the unit other than the unit represented by the general formula (1) that can be contained in the polymer of the present invention include a unit represented by the following general formula (6). Among them, a unit having a direct bond, an oxygen atom, and a methylene bond is preferably used because of the ease of crystallization.

[In the formula, m represents a number from 0 to ₃ , and R 3 and R ₄ independently form 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. Indicated, X is an independent direct bond, oxygen atom, sulfur atom, -SO-, -SO _2- , -CO-, -COO-, -CONH-, -CH = N-, -CH = CH. −, −CH = C (CH ₃ ) −, −CH ₂ −, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, _{−φ−, −CH 2} −φ−CH ₂ −, −CH (CH ₃ ) −φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−C (CH ₃ ) ₂ −, −CH ₂ −φ−φ−CH ₂ −, −CH (CH ₃ ) −φ−φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−φ−C (CH ₃ ) ₂ -or 9,9-fluorenyl group. Here, φ indicates a phenylene group. ]

The weight average molecular weight of the polymer of the present invention is 5,000 or more. When the molecular weight is less than 5,000, the resin composition using the resin composition is applied onto a substrate such as a copper foil, a SUS foil, a polyethylene terephthalate film, a polyimide film, or a glass plate and dried, or glass fiber. When a composite material obtained by impregnating a fiber base material such as carbon fiber is used, problems such as lack of strength and inferior dimensional stability are likely to occur. Further, when the molecular weight exceeds 200,000, even if diluted and dissolved with a solvent, the solution viscosity becomes too high at a concentration of 40% by weight to 70% by weight, which is generally used industrially, and the solution is applied to the substrate. , Or it becomes difficult to impregnate the fiber base material. 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 polymer of the present invention preferably has a reduced viscosity in the range of 0.2 to 1.2 dL / g, more preferably 0.3 to 0, when measured at 30 ° C. using N-methylpyrrolidone as a solvent. It is in the range of 0.8 dL / g. If it is lower than this, the film property may be deteriorated, and if it is larger than this, the handleability may be deteriorated.

The polymer of the present invention requires the unit of the general formula (1), and does not necessarily have to be a two-dimensional polymer, and may have a branched structure. The branched structure can be formed when the hydroxyl group of the general formula (1) reacts with an epoxy group, or when a trifunctional or higher functional epoxy resin or a curing agent is used in combination. It is preferable that the polymer having a branched structure also has thermoplasticity. The thermoplasticity not only improves the impact resistance of the molded product, but also enables secondary processing such as forming the sheet into a sheet and then forming the sheet into a molded product having a different shape. ..

The polymer of the present invention may take an amorphous glass state in a supercooled state, but at least a part of the polymer needs to be crystallized, and the degree of crystallization can be grasped by differential scanning calorimetry. .. Specifically, the peak (endothermic peak) of the endothermic curve associated with melting of the crystal in the differential scanning calorimetry measured at a heating rate of 10 ° C./min is measured, and the temperature is used as the melting point, and this endothermic peak curve is used. The heat of fusion is calculated from the integrated value of. Here, the preferred heat of fusion is 5 joules / g or more (hereinafter, may be referred to as “j / g”), preferably 10 j / g or more, and more preferably 30 j / g or more. If it is lower than this, the properties such as heat resistance, high thermal conductivity, low thermal expansion, low hygroscopicity, and high toughness based on crystallinity are not sufficient. Further, the preferable melting point range is that the endothermic peak temperature when measured at a heating rate of 10 ° C./min using a differential scanning heat analyzer is in the range of 100 ° C. to 350 ° C. If it is lower than this, the characteristics such as heat resistance and low thermal expansion based on crystallinity are not sufficient, and if it is higher than this, the handleability is lowered.

The degree of crystallinity of the polymer of the present invention can be generally adjusted by annealing at a temperature equal to or lower than the melting point. The annealing conditions are preferably carried out at a temperature 10 ° C. to 100 ° C. lower than the melting point and in the range of 5 minutes to 12 hours. In some cases, crystallization can be carried out by adding a solvent, a low molecular weight epoxy or the like.

Examples of the terminal group of the polymer of the present invention include an epoxy group, a hydroxyl group, a carboxylic acid, an amino group, a vinyl group, a mercapto group and an aromatic group, and an epoxy group is preferable.

The method for producing the polymer of the present invention is generally a method by a direct reaction between a dihydric phenol compound and epichlorohydrin, or a method by an addition polymerization reaction between a diglycidyl ether compound and a dihydric phenol compound. The polymer of the present invention may be produced by any production method, but if the polymer has low crystallinity, it will be in a supercooled state and the crystallinity will not increase. However, there is a problem that crystals are already precipitated in the state of a low molecular weight polymer and the molecular weight of the polymer does not increase. Therefore, it is necessary to select a desirable polymerization method and polymerization condition according to the characteristics of the target polymer. Each manufacturing method is shown below.

In the case of a direct reaction between a divalent phenol compound and epichlorohydrin, the bisphenol compound represented by the above general formula (5) is used as the divalent phenol compound, but the bisphenol compound of the general formula (5) is used in all. It is necessary to be 10 mol% or more of the dihydric phenol compound. If it is less than 10 mol%, the effect of introducing the benzophenone skeleton is not sufficient, and a molded product having heat resistance, high thermal conductivity, low thermal expansion, low hygroscopicity, and high toughness cannot be obtained.

In the case of the method by the addition polymerization reaction of the diglycidyl ether compound and the dihydric phenol compound, the dihydric phenol compound represented by the above general formula (3) or (5) and the above general formula (2) or (4) There is a method of reacting with the diglycidyl ether compound represented by. In this case, at least one of the divalent phenol compound represented by the general formula (5) or the diglycidyl ether compound represented by the general formula (2) is indispensable.

In the general formulas (1) to (5), R ₁ , R ₂ , R ₃ , and R ₄ are independently derived 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. It indicates the substituent of choice, preferably a hydrogen atom or a methyl group. When _{the carbon atom at the α-position of R 1} , R ₂ , R ₃ , and R ₄ is a secondary carbon or a tertiary carbon atom, the reactivity of the hydroxyl group may decrease, which is not preferable. Further, in the general formulas (1) to (5), the connecting positions of the benzene rings include the 1,4-position, the 1,3-position, and the 1,2-position, but the 1,4-position is particularly high. preferable. In the 1,3-position and 1,2-position, the crystallinity of the obtained polymer tends to decrease as compared with the 1,4-position, so that the heat resistance and high heat due to the crystallinity tend to decrease. Physical properties such as conductivity, low thermal expansion, low hygroscopicity, and high toughness tend to deteriorate.

In the general formula (3) or (4), X radicals are each independently a direct bond, an oxygen atom, a sulfur _{atom, -SO -, - SO 2 -} , - CO -, - COO -, - CONH-, -CH = N-, -CH = CH-, -CH = C (CH ₃ )-, -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -φ- , −CH ₂ −φ−CH ₂ −, −CH (CH ₃ ) −φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−C (CH ₃ ) ₂ −, −CH ₂ −φ −φ−CH ₂ −, −CH (CH ₃ ) −φ−φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−φ−C (CH ₃ ) ₂ − or 9,9 −fluorenyl Although it indicates a group (φ indicates a phenylene group), it is preferable that the molecule is easily oriented due to crystallization, there are few steric obstacles, and a direct bond with good symmetry, an oxygen atom, -CO-,- COO-, -CH _2- , -φ-.

Here, examples of the preferred divalent phenol compound represented by the general formula (3) include 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, and the like. Examples thereof include 1,3-bis (4-hydroxyphenoxy) benzene, 4,4'-bis (4-hydroxyphenoxy) diphenyl ether, 4,4'-dihydroxybenzophenone, and 4,4'-dihydroxydiphenyl sulfide. More preferably, it is 4,4'-dihydroxybiphenyl and 4,4'-dihydroxybenzophenone. These divalent phenol compounds can be used as a mixture.

In the case of the method by the addition polymerization reaction of the diglycidyl ether compound and the dihydric phenol compound, the diglycidyl ether compound represented by the general formula (2) is reacted with the dihydric phenol compound represented by the general formula (3). There is a method or a method of synthesizing by a method of reacting a diglycidyl ether compound represented by the general formula (4) with a dihydric phenol compound represented by the general formula (5). This reaction can be carried out in the presence of a catalyst such as an amine type, an imidazole type, a triphenylphosphine type or a phosphonium salt type. The molar ratio of the diglycidyl ether compound to the dihydric phenol compound is usually in the range of glycidyl ether compound: dihydric phenol compound = 3: 1 to 1: 3, preferably 2: 1 to 1: 2, and more preferably. Is 1.1: 1 to 1: 1.1. The closer the molar ratio of the diglycidyl ether compound to the divalent phenol compound is, the larger the molecular weight of the obtained polymer.

This reaction can be carried out without using a solvent, but a solvent may be used. Examples of the solvent include aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and cyclopentanone, aromatics such as benzene, toluene, orthoxylene, metaxylene, paraxylene, chlorobenzene and dichlorobenzene, and N. , N-dimethylformamide, N, N-dimethylacetamide, aliphatic amides such as N-methylpyrrolidone, ethers such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dimethyl sulfoxide and the like. Preferred organic solvents include cyclopentanone, cyclohexanone, diethylene glycol dimethyl ether, N, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide. Two or more kinds of these organic solvents may be selected and used as a mixed solvent.

This reaction can be carried out after mixing fillers such as silica, alumina, carbon powder, carbon fiber powder, carbon nanofibers and cellulose nanofibers. Further, the reaction may be carried out after impregnating a fiber base material such as glass fiber or carbon fiber with a mixture of a diglycidyl ether compound and a dihydric phenol compound in which a catalyst is added, or a preliminary reaction product thereof. As the method of impregnation, the above mixture or prereactant may be formed into a sheet or a block, and then powdered. Further, those dissolved or dispersed in a solvent may be used.

In this polymerization reaction, the diglycidyl ether compound and the dihydric phenol compound can be used as a mixture of two or more kinds, respectively, and the unit represented by the general formula (1) is 10 mol in the obtained polymer. It is necessary to select the diglycidyl ether compound and the dihydric phenol compound so as to be% or more. If the unit represented by the general formula (1) is less than 10 mol%, the effect of introducing the benzophenone skeleton is not sufficient, and a cured product having heat resistance, low thermal expansion, high thermal conductivity, and toughness cannot be obtained, which is not preferable. ..

When the resin composition of the present invention uses a polymer of the present invention having a molecular weight of 5,000 or more by weight average molecular weight, the resin flow during molding may be small and the circuit embedding property may be slightly insufficient. many. In this case, another low molecular weight epoxy resin can be added in order to make the circuit embedding property sufficient. 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 terms of weight average molecular weight.

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

The low molecular weight epoxy resin is aromatic and has an epoxy equivalent of 100 g / eq to 2,000 g / g in order to ensure sufficient circuit embedding properties without deteriorating physical properties such as flexibility and heat resistance after curing. The one of eq is good. If the epoxy equivalent exceeds 2,000 g / eq, the effect of sufficiently improving the circuit embedding property cannot be obtained, and the crosslink density tends to be low, making it difficult to obtain a heat-resistant cured film. Further, in the aliphatic epoxy resin, the heat resistance is not sufficient even if the circuit embedding property can be obtained. Further, when the epoxy equivalent is less than 100 g / eq, the cross-linking density of the cured product becomes high, so that the shrinkage rate of the cured product becomes large, the deformation of the cured product becomes large, and the water absorption rate tends to be high. Therefore, the epoxy equivalent of the low molecular weight epoxy resin is preferably 130 g / eq to 1,500 g / eq, and more preferably 150 g / eq to 1,000 g / eq. Preferred low molecular weight epoxy resins include epoxy resins obtained by the reaction of divalent phenol represented by the above general formula (3) with epichlorohydrin, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and tetra. Examples thereof include methyl bisphenol F type epoxy resin and tetrabromo bisphenol A type epoxy resin, but the present invention is not particularly limited thereto. These epoxy resins may be used alone or in combination of two or more.

Further, in the present invention, another high molecular weight epoxy resin can be added in order to have sufficient film properties.

In this case, the weight mixing ratio of the polymer of the present invention and the high molecular weight epoxy resin is 10 parts by weight to 90 parts by weight with respect to 100 parts by weight of the total amount of the polymer of the present invention and the high molecular weight epoxy resin. The range is preferably in the range of 20 parts by weight, more preferably in the range of 20 parts by weight to 60 parts by weight. If it is less than this, the effect of addition cannot be expected for flexibility, heat resistance, low thermal expansion and high thermal conductivity.

The preferred molecular weight of the high molecular weight epoxy resin is 5,000 to 100,000, more preferably 10,000 to 60,000 in weight average molecular weight, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetra. Examples thereof include methyl bisphenol F type epoxy resin and tetrabromo bisphenol A type epoxy resin, but the present invention is not particularly limited thereto.

It is advantageous that the resin composition of the present invention 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 curing agent, all commonly known curing agents can be used. For example, dicyandiamide and its derivatives, imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole and their derivatives, and divalents such as bisphenol A, bisphenol F, brominated bisphenol A, naphthalenediol and dihydroxybiphenyl. Novolak type phenol resin obtained by condensation reaction of phenol compounds such as phenol, cresol, bisphenol A, naphthol, naphthalenediol and aldehydes such as formaldehyde and ketones, phenol, cresol, bisphenol A, naphthol, Phenolic compounds such as aralkyl-type phenol resins obtained by condensation reaction of phenols such as naphthalenediol and xylylene glycols, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, hexahydroanhydrous Acid anhydride compounds such as phthalic acid, amine compounds such as polyamide amine obtained by condensation reaction between polyamines and acids such as diaminodiphenylmethane, triethylenetetramine, isophoronediamine and dimeric acid, and adipic acid. Examples thereof include commonly used hardeners for epoxy resins such as hydrazides such as dihydrazide and dihydrazide isophthalate, but the present invention is not particularly limited thereto. These curing agents may be used alone or in combination of two or more.

A solvent may be used for the resin composition in the present invention, preferably the epoxy resin composition, in order to maintain an appropriate viscosity when applied to a substrate. The solvent for adjusting the viscosity is preferably one that does not remain in the epoxy resin composition when the solvent is dried at 80 ° C. to 200 ° C., specifically, 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 and the like, but are not particularly limited thereto. These solvents may be used alone or in combination of two or more.

Silica, calcium carbonate, talc, aluminum hydroxide, mica, alumina, aluminum nitride, carbon powder, etc. are added to this resin composition in order to impart heat resistance and flame retardancy, reduce thermal expansion rate, increase thermal conductivity, and the like. , Carbon fiber powder, carbon nanofibers, cellulose nanofibers and the like, and epoxy silane coupling agent, rubber component and the like may be added to improve the adhesive strength to the extent that the physical properties of the molded product are not deteriorated.

A curing accelerator may be used in the resin composition of the present invention, if necessary. For example, various known curing accelerators such as amine type, imidazole type, triphenylphosphine type, and phosphonium salt type can be used, but the present invention is not particularly limited thereto. When a curing accelerator is used, it is preferably in the range of 0.01 wt% to 10 wt% with respect to the resin component. If it exceeds 10 wt%, there is a concern that the storage stability may deteriorate, which is not preferable.

The resin composition of the present invention is molded by transfer molding, compression molding, or casting a resin solution dissolved or dispersed in a solvent onto a metal foil, or the resin solution is formed of glass fiber, carbon fiber, aramid fiber, or the like. A resin molded product can be obtained by impregnating a base material into a prepreg and press-molding it, but it is usually desirable to cast-mold or press-mold as a prepreg on the base material. In particular, 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 with the above-mentioned solvent so as to have a constant curing time. An appropriate amount of curing agent is added to the prepreg, and if necessary, a curing accelerator is added to form a varnish, which is applied to a base material to volatilize the solvent at 100 ° C. to 160 ° C. to form a prepreg, and the obtained prepreg is heated to form a molded product. can do.

Next, the present invention will be specifically described based on Examples. The present invention is not limited to this specific example, and any modification or modification is possible as long as it does not deviate from the gist of the present invention.
The evaluation method of the physical properties shown in the examples is as follows.

(1) Hydrolyzable chlorine: 0.5 g of the epoxy resin A described later as a sample is dissolved in 30 ml of dioxane, 1N-KOH and 10 ml are added, boiled and refluxed for 30 minutes, cooled to room temperature, and further 80% acetone water. 100 ml was added, and the mixture was measured by potentiometric titration with a _{0.002N-AgNO 3 aqueous solution.}
(2) Melting point and heat of fusion: The peak temperature of the endothermic curve obtained at a heating rate of 10 ° C./min using a differential thermal analyzer was taken as the melting point, and the integrated value of the endothermic peak curve was taken as the heat of fusion.
(3) Thermal deformation temperature; measured according to JIS-7191.
(4) GPC measurement: Using a 515A type device manufactured by Japan Waters Corp., columns; TSK-GEL2000 x 3 and TSK-GEL4000 x 1 [both manufactured by Toso Co., Ltd.], solvent; tetrahydrofuran, Flow rate: 1 ml / min, temperature: 38 ° C., detector; measured according to RI conditions.
(5) Measurement of glass transition point and coefficient of linear expansion: Measurement was performed at a heating rate of 10 ° C./min using a TMA120C type thermomechanical measuring device manufactured by Seiko Instruments Inc.
(6) Thermal conductivity: Measured by the transient hot wire method using an LFA447 type thermal conductivity meter manufactured by NETZSCH.

[Reference example]
1070 g of 4,4'-dihydroxybenzophenone was dissolved in 6500 g of epichlorohydrin, and 808 g of a 48% sodium hydroxide aqueous solution was added dropwise at 60 ° C. under reduced pressure (about 130 Torr) over 4 hours. During this period, the produced water was removed from the system by azeotropic boiling with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropping, the reaction was continued for another 1 hour to dehydrate, epichlorohydrin was distilled off, 3500 g of methyl isobutyl ketone was added, and the mixture was washed with water to remove salts. Then, 100 g of 20% sodium hydroxide was added at 80 ° C., the mixture was stirred for 2 hours, and washed with 1000 mL of warm water. Then, after removing water by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 1460 g of a pale yellow crystalline epoxy resin (epoxy resin A).

The melting point of the epoxy resin A was 128 ° C. The viscosity at 150 ° C. was measured using an ICI cone plate viscometer and found to be 11.6 mPa · s. The epoxy equivalent was measured by JIS K 7236 and found to be 179 g / eq, the hydrolyzable chlorine was 270 ppm, and the component ratios obtained from the GPC measurement of the obtained resin were in the structure of the general formula (2). R ₁ and R ₂ were hydrogen atoms, n was 1 in 91.0% of the compounds, and their dimer was 8.2%.

[Example 1]
179 parts of epoxy resin A, 107 parts of 4,4'-dihydroxybenzophenone, and 300 parts of N-methylpyrrolidone synthesized in the reference example were placed in a 500 ml glass separable flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction device. After measuring, heating to 110 ° C. with stirring under a nitrogen stream to uniformly dissolve, 0.2 part of 2-ethyl-4-methylimidazole was added as a catalyst, and the mixture was reacted at 150 ° C. for 5 hours to prepare a polymer solution. Got The obtained polymer solution was added dropwise to a large amount of methanol to recover 262 g of the precipitated white polymer (polymer A). The reduced viscosity of the obtained polymer measured at 30 ° C. using N-methylpyrrolidone as a solvent was 0.43 dL / g. Since the obtained polymer A has a high molecular weight, it is not completely dissolved in THF. Therefore, when only the soluble portion was measured by GPC, the weight average molecular weight was 8300.
Further, FIG. 1 shows a DSC chart of polymer A obtained at a heating rate of 10 ° C./min using a differential thermal analyzer. The peak melting point was observed at 229.4 ° C. and the heat of fusion was 19.2 j / g. This was measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC6200 type manufactured by Seiko Instruments Inc.). Further, FIG. 2 shows the results of measuring the infrared absorption spectrum using an infrared spectrophotometer. From the result of FIG. 2, ^{a peak of 1645 cm -1} derived from an aromatic ketone group is confirmed, and it can be confirmed that the polymer has an aromatic ketone group. In Example 1, as described above, since the epoxy resin A having a benzophenone structure and the 4,4'-dihydroxybenzophenone were reacted with each other, the above formula (1) in the obtained polymer A was used. The unit represented is approximately 100 mol%.

[Example 2]
Using 93 parts of 4,4'-dihydroxybiphenyl instead of 4,4'-dihydroxybenzophenone, the reaction was carried out in the same manner as in Example 1 to obtain 251 parts of the polymer (polymer B). The reduced viscosity of the obtained polymer at 30 ° C. using N-methylpyrrolidone as a solvent was 0.41 dL / g. Further, FIG. 3 shows a DSC chart of the polymer B when measured in the same manner as in the case of the polymer A. The peak melting point obtained by differential scanning calorimetry was observed at 244.7 ° C, and the heat of fusion was 35.8 j / g. In Example 2, instead of 4,4'-dihydroxybenzophenone in Example 1, the same molar amount of 4,4'-dihydroxybiphenyl was used, and the mixture was reacted with epoxy resin A in approximately the same molar amount. Therefore, it is estimated that the unit represented by the above formula (1) is about 50 mol% in the obtained polymer B.

Other Physical Properties Each polymer obtained in Examples 1 and 2 and a bisphenol A type phenoxy resin as a comparative example [YP-50; manufactured by Nittetsu Chemical & Materials Co., Ltd., weight average molecular weight 70,000, polymer C] A test piece was prepared as a polymer by press molding and used for various physical property evaluations. The results are also shown in Table 1.

Claims (9)

The following general formula (1),

(In the formula, 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 n is a number of 1 to 3 An aromatic ketone type polymer having a ratio of units represented by (shown) of 10 to 100 mol%, a weight average molecular weight of 5,000 or more, and crystallinity. _{The aromatic according to claim 1} , wherein in the general formula (1), the benzene ring has a 1,4-phenylene structure, R 1 and R ₂ are both hydrogen atoms, and n is 1. Group ketone type polymer. The aromatic ketone type polymer according to claim 1 or 2, wherein the peak temperature of the endothermic curve associated with melting of the crystal in the differential scanning calorimetry measured at a heating rate of 10 ° C./min is in the range of 100 ° C. to 350 ° C. The aromatic ketone type weight according to any one of claims 1 to 3, wherein the integral value of the endothermic peak curve associated with melting of the crystal in the differential scanning calorimetry measured at a heating rate of 10 ° C./min is 10 joules / g or more. Combined. A resin composition comprising the aromatic ketone type polymer according to any one of claims 1 to 4. A resin molded product obtained by molding the resin composition according to claim 5. The method for producing an aromatic ketone type polymer according to any one of claims 1 to 4.
The following general formula (2),

(In the formula, 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 n is a number of 1 to 3 The diglycidyl compound represented by (shown) and the following general formula (3),

[In the formula, m represents a number from 0 to ₃ , and R 3 and R ₄ independently form 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. Indicated, X is an independent direct bond, oxygen atom, sulfur atom, -SO-, -SO _2- , -CO-, -COO-, -CONH-, -CH = N-, -CH = CH. −, −CH = C (CH ₃ ) −, −CH ₂ −, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, _{−φ−, −CH 2} −φ−CH ₂ −, −CH (CH ₃ ) −φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−C (CH ₃ ) ₂ −, −CH ₂ −φ−φ−CH ₂ −, −CH (CH ₃ ) −φ−φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−φ−C (CH ₃ ) ₂ -or 9,9-fluorenyl group. Here, φ indicates a phenylene group. ] A method for producing an aromatic ketone type polymer, which comprises reacting with a bisphenol compound represented by. The method for producing an aromatic ketone type polymer according to any one of claims 1 to 4.
The following general formula (4),

[In the formula, m represents a number from 0 to ₃ , and R 3 and R ₄ independently form 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. Indicated, X is an independent direct bond, oxygen atom, sulfur atom, -SO-, -SO _2- , -CO-, -COO-, -CONH-, -CH = N-, -CH = CH. −, −CH = C (CH ₃ ) −, −CH ₂ −, −CH (CH ₃ ) −, −C (CH ₃ ) ₂ −, _{−φ−, −CH 2} −φ−CH ₂ −, −CH (CH ₃ ) −φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−C (CH ₃ ) ₂ −, −CH ₂ −φ−φ−CH ₂ −, −CH (CH ₃ ) −φ−φ−CH (CH ₃ ) −, −C (CH ₃ ) ₂ −φ−φ−C (CH ₃ ) ₂ -or 9,9-fluorenyl group. Here, φ indicates a phenylene group. ], And the following general formula (5),

(In the formula, 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 n is a number of 1 to 3. A method for producing an aromatic ketone type polymer, which comprises reacting with a bisphenol compound represented by). The method for producing an aromatic ketone type polymer according to any one of claims 1 to 4.
The following general formula (5),

(In the formula, 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 n is a number of 1 to 3 A method for producing an aromatic ketone type polymer, which comprises reacting a bisphenol compound represented by (shown) with epichlorohydrin in the presence of an alkali metal hydroxide.

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