WO2024029602A1

WO2024029602A1 - Resin composition, and cured product

Info

Publication number: WO2024029602A1
Application number: PCT/JP2023/028470
Authority: WO
Inventors: 昌己大村; 浩一郎大神
Original assignee: 日鉄ケミカル＆マテリアル株式会社
Priority date: 2022-08-05
Filing date: 2023-08-03
Publication date: 2024-02-08

Abstract

The present invention provides: a cured molded product having excellent moldability and reliability, and having high thermal conductivity, low water absorption, low thermal expansion, high heat resistance, and flame retardancy; in addition, a resin composition having excellent solvent solubility, and being used for laminating, molding, casting, adhesion, etc.; and a cured product thereof. The cured product has excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy. This resin composition comprises at least a crystalline resin and an additive, the resin composition being characterized in that the additive is a layered clay mineral and contains 1-20 parts by weight of the layered clay mineral with respect to 100 parts by weight of the resin component, wherein the melting point of the crystalline resin has 80 °C-200 °C (exclusive of 80 °C). Also provided is a cured product of the resin composition.

Description

Resin composition and cured product

The present invention relates to a resin composition useful as an insulating material for electrical and electronic materials such as semiconductor encapsulation, laminates, and heat dissipating substrates with excellent reliability, and a cured product using the same.

Conventionally, as methods for sealing electrical and electronic components such as diodes, transistors, and integrated circuits, as well as semiconductor devices, there have been methods for sealing with epoxy resins, silicone resins, etc., and hermetic sealing methods using glass, metals, ceramics, etc. However, in recent years, resin encapsulation using transfer molding has become mainstream, as it has improved reliability, can be mass-produced, and has cost advantages.

In the resin composition used for resin sealing by transfer molding, a sealing material consisting of an epoxy resin and a resin composition whose main components are a phenol resin as a curing agent is generally used.

Epoxy resin compositions used to protect elements such as power devices are densely packed with inorganic fillers such as crystalline silica to cope with the large amount of heat emitted by the elements.

Power devices include those that are composed of a single chip incorporating IC technology and those that are modularized, and further improvements in heat dissipation, heat resistance, and thermal expansion properties of sealing materials are desired. There is.

In addition, high-speed communication technology is being actively researched to improve the signal transmission speed of printed circuit boards, encapsulants, casting materials, etc. used in communication equipment as the communication speed and amount of communication increases. For electronic materials used in such applications, materials that can reduce dielectric loss are required, and for printed circuit board applications, curable resins that can be multilayered are also required.

On the other hand, electronic processing components that process such large amounts of data generate a lot of heat, and heat accumulation can cause problems such as a slowdown in the processing speed of electronic processing components, so technology has been developed to appropriately cool printed circuit boards using heat sinks, etc. Various methods are known, such as a method of incorporating a heat transfer member such as a copper coin or a copper inlay (Patent Document 1), and a method of using a special shape of the filler to be mixed (Patent Document 2). However, such a method was undesirable because it led to an increase in weight and an increase in the size of the equipment.

In addition, in order to increase the thermal conductivity of encapsulant compositions, a method is used to remove heat from electronic processing components by considering the type and amount of various fillers. Attempts have been made to include inorganic fillers such as crystalline silica, silicon nitride, aluminum nitride, and spherical alumina powder (Patent Documents 3 and 4). However, when the content of the inorganic filler is increased, the viscosity during molding increases and the fluidity decreases, causing a problem that moldability is impaired. Therefore, there are limits to the method of simply increasing the content of inorganic fillers.

Based on the above background, methods of improving the thermal conductivity of the composition by increasing the thermal conductivity of the matrix resin itself are also being considered. For example, liquid crystalline epoxy resins having rigid mesogenic groups and epoxy resin compositions using the same have been proposed (Patent Documents 5 and 6). However, as the curing agent used in these epoxy resin compositions, aromatic diamine compounds are used, and there is a limit to increasing the filling rate of the inorganic filler, and there are also problems in terms of electrical insulation. Furthermore, when an aromatic diamine compound was used, although the liquid crystallinity of the cured product could be confirmed, the degree of crystallinity of the cured product was low, and it was not sufficient in terms of high thermal conductivity, low thermal expansion, low hygroscopicity, etc. Furthermore, in order to exhibit liquid crystallinity, it was necessary to apply a strong magnetic field to orient the molecules, and there were major restrictions in terms of equipment for widespread industrial use. In addition, in a compound system with an inorganic filler, the thermal conductivity of the inorganic filler is overwhelmingly higher than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is high, the thermal conductivity of the inorganic filler is overwhelmingly higher than that of the matrix resin. The reality is that they do not significantly contribute to improving thermal conductivity, and existing resins have not been able to sufficiently improve thermal conductivity.

Layered clay minerals such as talc are generally used to improve fluidity and reduce the coefficient of linear expansion. A formulation in which layered clay minerals are combined with an inorganic filler having high thermal conductivity has been proposed, but the high thermal conductivity is achieved by contact between the inorganic substances and does not act on the matrix resin itself (Patent Document 7).

Patent Document 8 discloses a tetrafunctional or higher functional vinyl resin having a biphenyl skeleton as a polyfunctional vinyl resin that has both high thermal conductivity and low dielectric loss tangent. There is no mention of the solvent solubility of the hydroxyl resin, and no mention is made of the influence of impurities such as remaining polar groups on thermal conductivity.

Japanese Patent Application Publication No. 2009-170493 International publication WO2013/100172 Japanese Patent Application Publication No. 11-147936 Japanese Patent Application Publication No. 2002-309067 Japanese Patent Application Publication No. 11-323162 Japanese Patent Application Publication No. 9-118673 International publication WO2013/100174 International Publication WO2021/200414

Therefore, an object of the present invention is to provide a resin composition and a cured product thereof that can solve the above problems.
For example, the epoxy resin composition according to the first embodiment described below can produce molded products that have excellent moldability, reliability, high thermal conductivity, low thermal expansion, heat resistance, moisture resistance, and flame retardancy. Furthermore, a molded article whose crystallinity can be observed by XRD is provided.
In addition, for example, the vinyl resin composition according to the second embodiment described below has excellent solvent solubility and moldability, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and low dielectric loss tangent. Provided are vinyl resin compositions and cured products thereof that provide cured products with excellent flammability and are useful for sealing electrical and electronic components, circuit board materials, and the like.

Through intensive studies, the present inventors have found that a resin composition containing layered clay minerals is expected to solve the above problems, and that a cured product thereof exhibits an effect on at least thermal conductivity, and It has been found that, in some cases, it exhibits effects such as low dielectric constant and low dielectric loss tangent.

That is, the gist of the present invention is as follows.
[1] A resin composition containing at least a crystalline resin and an additive, where the additive is a layered clay mineral and contains 1 to 20 parts by weight of the layered clay mineral based on 100 parts by weight of the resin component. ,
A resin composition characterized in that the crystalline resin has a melting point of more than 80°C and less than 200°C.
[2] The resin composition according to [1], wherein the additive is talc or mica.
[3] The resin composition according to [2], wherein the additive is talc.
[4] The resin composition according to [1], wherein the crystalline resin is an epoxy resin and/or a vinyl resin.
[5] The resin composition according to [4], wherein the crystalline resin is an epoxy resin with a melting point of more than 80°C and 180°C or less and/or a vinyl resin with a melting point of 90 to 200°C.
[6] The crystalline resin is an epoxy resin, contains a curing agent, and when measured by X-ray diffraction (XRD) of a cured product of the resin composition, diffraction occurs in a region with a diffraction angle 2θ of 15° or more and less than 25°. The resin composition according to any one of [1] to [5], wherein a peak is detected.
[7] The resin composition according to [6], wherein the epoxy resin is represented by the following general formula (1-1) or (1-2).

(In formula (1-1), G represents a glycidyl group, and A is independently a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, or a divalent carbon number of 1 to 6 represents a hydrocarbon group, and n represents a number from 0 to 20.)

(In formula (1-2), Y is independently a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ - or -C( CH ₃ ) ₂ -. B independently represents a benzonitrile structure or -(CH ₂ ) _q -, p represents a number from 0 to 15, and q represents a number from 3 to 10.)
[8] The crystalline resin is a vinyl resin, and the vinyl resin is characterized by having a vinyl equivalent of 150 to 1000 g/eq, a hydroxyl equivalent of 5000 g/eq or more, and a total chlorine amount of 2000 ppm or less [1] The resin composition according to any one of ~[5].
[9] The resin composition according to [8], wherein the vinyl resin is represented by one or more of the following general formulas (2-1) to (2-3).

(In formula (2-1), R ¹ to R ⁶ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.)

(In formula (2-2), A independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, or a divalent hydrocarbon group having 1 to 6 carbon atoms, and are independently a benzene ring, a naphthalene ring or a biphenyl ring, and n represents a number from 0 to 20.)

(In formula (2-3), Y is independently a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ - or -C( CH ₃ ) ₂ -. B independently represents a benzonitrile structure or -(CH ₂ ) _q -, p represents a number from 0 to 15, and q represents a number from 3 to 10.)
[10] The resin composition according to any one of [1] to [5], which contains 20 to 90 wt% of an inorganic filler excluding layered clay minerals.
[11] The resin composition according to any one of [1] to [5], which is a resin composition that provides a cured product with high thermal conductivity.
[12] The resin composition according to [6], which is a resin composition that provides a cured product for high thermal conductivity having a degree of crystallinity of 10% or more.
[13] A cured product obtained by curing the resin composition according to any one of [1] to [5].

The resin composition of the present invention provides, for example, a cured molded product with excellent moldability and reliability, as well as high thermal conductivity, low water absorption, low thermal expansion, high heat resistance, and flame retardance. In addition, for example, it has excellent solvent solubility and is suitable for resin compositions and their cured products used for applications such as lamination, molding, casting, and adhesives, and this cured product has heat resistance, thermal decomposition stability, and thermal conductivity. , low dielectric constant, low dielectric loss tangent, and excellent flame retardancy.

1 is an XRD profile of a cured molded product of the epoxy resin composition obtained in Example 1-1 in the first embodiment. 1 is an XRD profile of a cured molded product of an epoxy resin composition obtained in Comparative Example 1-1 in the first embodiment. 2 is a GPC chart of vinyl resin A obtained in Synthesis Example 2-1 in the second embodiment. 2 is a GPC chart of vinyl resin B obtained in Synthesis Example 2-2 in the second embodiment. 2 is a GPC chart of vinyl resin C obtained in Synthesis Example 2-3 in the second embodiment. It is an FD-MS spectrum of vinyl resin C obtained in Synthesis Example 2-3 in the second embodiment.

Hereinafter, the present invention will be explained in detail. In detail, as will be described later, the first embodiment and the second embodiment will be described as examples.

The resin composition of the present invention is a resin composition containing at least a crystalline resin and an additive, wherein the additive is a layered clay mineral, and the layered clay mineral is added in an amount of 1 to 100 parts by weight based on 100 parts by weight of the resin component. 20 parts by weight of the crystalline resin, and the melting point of the crystalline resin is above 80°C and below 200°C.

The resin used in the resin composition of the present invention is a crystalline resin that has crystallinity at room temperature. Here, the term "crystalline resin" has the same meaning as commonly used in the art, and is a resin having a crystalline structure. Furthermore, the term "crystalline resin" refers to a resin that exhibits a clear endothermic peak in differential scanning calorimetry.

The crystalline resin is not limited and can be appropriately selected depending on the purpose, and examples thereof include acrylic resin, styrene-acrylic resin, polyester resin, epoxy resin, and vinyl resin. These resins may be used alone or in combination of two or more. Among these crystalline resins, considering the above-mentioned properties aimed at by the present invention, moldability, reliability, high thermal conductivity, low water absorption, heat resistance, low thermal expansion, heat resistance, moisture resistance, difficulty From the viewpoint of flammability, epoxy resin is preferred. Furthermore, vinyl resin is preferred because it has excellent solvent solubility, moldability, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy.

The crystalline resin of the present invention has a melting point. Its melting point range is more than 80°C and less than 200°C. Although it depends on the resin used, the temperature is preferably 90° C. or higher in order to improve thermal conductivity, reliability, and heat resistance. Here, the melting point is the endothermic peak temperature associated with melting of the crystal in scanning differential thermal analysis. Resins with melting points higher than 200°C have strong crystallinity and tend to reduce solvent solubility and melt-kneading properties, while cured products using resins with melting points of 80°C or lower tend not to improve thermal conductivity. .

The layered clay minerals used as additives in the resin composition of the present invention are also called tabular particles, and specifically include talc, kaolin, mica, montmorillonite, beidellite, hectorite, saponite, nontronite, and stevensite. smectite minerals such as vermiculite, bentonite, kanemite, kenyanite, makanite, etc., layered sodium silicate such as vermiculite, bentonite, kanemite, kenyanite, makanite, Na type tetrasilicic fluorinated mica, Li type tetrasilicic fluorinated mica, Na type fluorinated teniolite, Li type fluorinated teniolite, etc. Contains mica group clay minerals; etc. These may be obtained from natural minerals or may be chemically synthesized. Furthermore, the surface of the layered clay mineral may be modified (surface treated) with an ammonium salt or the like. In particular, from the viewpoint of good thermal conductivity, a silicate compound containing magnesium is preferred, talc or mica is more preferred, and talc is even more preferred.

The layered clay mineral is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total resin component. It is preferably contained in an amount of 5 to 15 parts by weight. If the amount of layered clay mineral in the resin composition is too small, it may be difficult to sufficiently exhibit the above-mentioned thermal conductivity. On the other hand, if the content of the layered clay mineral is higher than this, fluidity and heat resistance may decrease. In addition, when containing a highly thermally conductive inorganic filler such as alumina, if the amount of layered clay minerals is large, the content of the highly thermally conductive inorganic filler may not be sufficient and the overall thermal conductivity may decrease. be. Here, the resin component refers to a resin and a component related to curing or modification thereof. For example, in the first embodiment described below, the resin component refers to an epoxy resin, a curing agent, and a curing accelerator included if necessary. Furthermore, in the second embodiment described below, the resin component refers to a vinyl resin and a radical polymerization initiator and a modifier included as necessary. The resin component can be used with appropriate changes depending on the purpose.

The resin composition of the present invention achieves the object of the present invention, except for using the crystalline resin having a melting point within the predetermined range and the layered clay mineral as an additive having a content within the predetermined range. , and there is no restriction as long as it does not impair the purpose of the present invention.
In order to describe specific embodiments of the present invention, a first embodiment using an epoxy resin as the crystalline resin and a second embodiment using a vinyl resin will be illustrated below. As mentioned above, epoxy resins and vinyl resins satisfy some of the characteristics aimed at by the present invention and are preferred embodiments, but the scope of the present invention is not limited to these embodiments. Not done.

<First embodiment>
The first embodiment of the present invention will be described in detail below.

First, the first embodiment of the present invention relates to an epoxy resin composition using an epoxy resin as a crystalline resin. In this first embodiment, the epoxy resin composition preferably contains a curing agent in addition to the above-mentioned additive (layered clay mineral) and epoxy resin. The curing agent will be described later. Regarding the epoxy resin composition of this first embodiment, it is a preferred embodiment that a diffraction peak is observed in a predetermined region in measurement (XRD) of the cured product by X-ray diffraction method, More specifically, it is preferable that the diffraction peak is detected in a region where the diffraction angle 2θ is 15° or more and less than 25°. Usually, the profile when XRD measurement of a cured epoxy resin consisting only of organic substances is broad, and no clear peak is detected. When crystallinity is exhibited, a sharp peak is detected, and the detection range is a range in which 2θ is 15° or more and less than 25°. Further, when the epoxy resin composition contains an inorganic substance, a peak of the inorganic substance is detected, but the peak position differs depending on the crystal structure and can be distinguished from the peak of the organic substance. When the additive (layered clay mineral) is talc, a diffraction peak is observed in the 2θ range of 28° to 29°. Here, a broad peak is also called an amorphous peak, and is a peak with a peak width of 8° or more, and a sharp peak is also called a crystalline peak, and is a peak with a width of 5° or less, preferably 3°. The peak is within °. That is, "a diffraction peak is detected" in the first embodiment preferably means that the sharp peak (crystalline peak) is detected in a range of 2θ of 15° or more and less than 25°. means. Note that the peak width can be determined by a normal peak analysis method performed by a person skilled in the art, and is usually parallel to the baseline and refers to the width between the starting point of the peak rise and the end point of the peak falling.

As described above, the epoxy resin component of the epoxy resin composition according to the first embodiment of the present invention has a melting point of more than 80°C and less than 200°C. A preferable lower limit is 83°C or higher, and a more preferable lower limit is 90°C or higher. On the other hand, a preferable upper limit is 180°C or less, and a more preferable upper limit is 150°C or less.

The epoxy resin component of the epoxy resin composition according to the first embodiment of the present invention may be any epoxy resin having two or more epoxy groups in the molecule. Examples include bisphenol A, bisphenol F, 4,4'-dihydroxydiphenyl ether, hydroquinone, 4,4'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, fluorene bisphenol, 2,2'-biphenol, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, allylated bisphenol A, allylated bisphenol F, divalent phenols such as allylated phenol novolak, or phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, tris- (4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4- Raw materials such as trivalent or higher phenols such as benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, or halogenated bisphenols such as tetrabromobisphenol A There are glycidyl ether compounds derived from phenolic compounds. These epoxy resins can be used alone or in combination of two or more. Furthermore, one type or two or more types of epoxy resins having mesogenic groups can be used.

As the epoxy resin, highly thermally conductive epoxy resins having rigid structures such as 4,4'-dihydroxydiphenyl ether, hydroquinone, glycidyl ether derivatives derived from 4,4'-dihydroxybiphenyl, and mesogenic skeletons are preferred, and in particular, the above-mentioned epoxy resins are preferred. Epoxy resins represented by general formula (1-1) or (1-2) are more preferred. These highly thermally conductive epoxy resins preferably contain 50 wt% or more of the entire epoxy resin component. More preferably, it is 70 wt% or more. If the usage ratio is less than this, the effect of improving heat resistance, thermal conductivity, etc. when the epoxy resin is cured may be small.

In the above general formula (1-1), n is the number of repetitions (number average) and represents a number from 0 to 20. Preferably, it is a mixture of components having different values of n. Further, G represents a glycidyl group, and A independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, or a divalent hydrocarbon group having 1 to 6 carbon atoms. A is preferably a single bond from the viewpoint of thermal conductivity.

In the above general formula (1-2), p is the number of repetitions (number average) and represents a number from 0 to 15. Preferably, it is a mixture of components having different values of p. Moreover, Y independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ - or -C(CH ₃ ) ₂ - . From the viewpoint of high thermal conductivity, Y preferably has a single bond biphenyl structure, -SO ₂ -, -CO-, -COO-, or -CONH-, and a biphenyl structure at the 4,4' position is particularly preferred. On the other hand, in terms of moldability and solvent solubility, Y is preferably an oxygen atom, a sulfur atom, -CH ₂ -, or -C(CH ₃ ) ₂ -. Further, B in formula (1-2) independently represents a benzonitrile structure or -(CH ₂ ) _q -, and q represents a number from 3 to 10. Preferred B has both structures in at least one molecule.

The method for producing the epoxy resin used in the epoxy resin composition according to the first embodiment of the present invention is not particularly limited, and it can be produced by reacting a raw material phenolic compound with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction. The raw material phenolic compound can be selected according to the epoxy resin to be obtained, as described above. In particular, the epoxy resin represented by the above formula (1-1) or (1-2) can be produced as follows.

The epoxy resin represented by the formula (1-1) can be produced by reacting a polyhydric hydroxy resin (raw material phenolic compound) represented by the following formula (1-3) with epichlorohydrin.

Here, A and n in formula (1-3) are the same as in formula (1-1) above.

This polyhydric hydroxy resin (1-3) is reacted with an aromatic crosslinking agent having a biphenyl structure represented by formula (1-4) and a bifunctional phenol compound represented by formula (1-5). It can be manufactured by

Here, Z in formula (1-4) represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms.

Here, A in formula (1-5) is the same as in formula (1-1) above.

In the aromatic crosslinking agent represented by the above formula (1-4), Z represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. Specific examples of the aromatic crosslinking agent include 4,4'-bishydroxymethylbiphenyl, 4,4'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, and 4,4'-bismethoxymethylbiphenyl. , 4,4'-bisethoxymethylbiphenyl. From the viewpoint of reactivity, 4,4'-bishydroxymethylbiphenyl or 4,4'-bischloromethylbiphenyl is preferable, and from the viewpoint of reducing ionic impurities, 4,4'-bishydroxymethylbiphenyl or 4,4'-bishydroxymethylbiphenyl is preferable. , 4'-bismethoxymethylbiphenyl is preferred.

Further, as the difunctional phenol compound of formula (1-5), specifically, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ketone, 4,4' -dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, dihydroxydiphenylmethanes, 2,2-bis(4-hydroxyphenyl)propane, especially 2,2'-dihydroxybiphenyl, 4, from the viewpoint of solvent solubility. , 4'-dihydroxydiphenyl ether, and dihydroxydiphenylmethane are preferred. The dihydroxydiphenylmethane may be a mixture of ortho, meta, and para, but preferably has an isomer ratio of 4,4'-dihydroxydiphenylmethane of 40% or less. If there is a large amount of 4,4'-dihydroxydiphenylmethane, the crystallinity will be strong and there is a concern that the solvent solubility will decrease.

The molar ratio when the aromatic crosslinking agent of formula (1-4) and the phenol compound of formula (1-5) are reacted is generally 1 mole of the phenol compound to 0.00% of the aromatic crosslinking agent. The amount is in the range of 2 to 0.7 mol, more preferably 0.4 to 0.7 mol. This reaction can be carried out without a catalyst or in the presence of an acid catalyst such as an inorganic acid or an organic acid. When using 4,4'-bischloromethylbiphenyl, the reaction can be carried out without a catalyst, but in general, it is necessary to suppress side reactions such as the formation of ether bonds due to the reaction of chloromethyl groups and hydroxyl groups. It is preferable to carry out the reaction in the presence of an acidic catalyst. This acidic catalyst can be appropriately selected from well-known inorganic acids and organic acids, such as mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and metasulfonic acid. Examples include organic acids such as acids, trifluorometasulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids.

This reaction is usually carried out at 100 to 250°C for 1 to 20 hours. The temperature is preferably 100 to 180°C, more preferably 140 to 180°C. If the reaction temperature is low, the reactivity is poor and it takes time, and if the reaction temperature is high, there is a risk of decomposition of the resin.

As a solvent during the reaction, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc. Among these, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, etc. are particularly preferred. After completion of the reaction, the solvent may be removed from the obtained polyhydric hydroxy resin by distillation under reduced pressure, washing with water, reprecipitation in a poor solvent, etc., but the solvent may be left as a raw material for the epoxidation reaction. May be used.

The polyhydric hydroxy resin of formula (1-3) thus obtained can be used not only as a raw material for epoxy resin but also as an epoxy resin curing agent. Moreover, by further combining it with a curing agent such as hexamine, it can be applied as a phenolic resin molding material.

Next, the method for producing the epoxy resin represented by the formula (1-2) is not particularly limited, but by reacting the raw material phenolic compound represented by the following formula (1-6) with epichlorohydrin. can be manufactured. This reaction can be carried out in the same manner as a normal epoxidation reaction. Furthermore, when the raw material is a mixture with a compound of p=0 or 1 represented by the formula (1-6), the epoxy resin obtained by this production method can be used as described in the first embodiment of the present invention. This includes not only an epoxy resin but also a mixture of the epoxy resin of the first embodiment of the present invention and an epoxidized compound of p=0 or 1 represented by the above general formula (1-2).

Here, Y, B, and p in formula (1-6) are the same as in formula (1-2) above.
The phenolic compound represented by formula (1-6) (including the case where it is a mixture with a compound where p = 0 or 1) has a hydroxyl equivalent (g/eq) of preferably 150 to 230, more preferably It is 170-220. Further, the melting point is preferably 140°C to 300°C, more preferably 150°C to 250°C.

Here, the manufacturing method for the raw material phenolic compound represented by formula (1-6) is not limited as long as it has a predetermined structure, but it can be prepared by combining either or both of a benzonitrile compound and a dihalogen alkyl compound with formula (1-6). -6) is suitably obtained by reacting with a dihydroxy compound having a Y group in the presence of a basic catalyst.
For example, examples of the benzonitrile compound include 2,4-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,6-dichlorobenzonitrile, 3,5-dichlorobenzonitrile, 2,4-dibromobenzonitrile, Examples include 2,5-dibromobenzonitrile, 2,6-dibromobenzonitrile, 3,5-dibromobenzonitrile, and examples of the dihalogen alkyl compound include 1,3-dibromopropane, 1,4-dibromobutane, Examples of the dihydroxy compound having a Y group in formula (1-6) include 1,5-dibromopentane and 1,6-dibromohexane, such as 4,4'-dihydroxybiphenyl, 4,4'- Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, bisphenol A, bisphenol F and the like.
The method for producing the raw material phenolic compound is not particularly limited, but for more detailed specific conditions, for example, the production method described in WO2021/201046 can be used.

The reaction between the above-mentioned raw material phenolic compound and epichlorohydrin can be carried out, for example, by dissolving the phenolic compound in excess epichlorohydrin, and then heating the mixture at 50 to 150°C in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Preferably, a method in which the reaction is carried out at a temperature in the range of 60 to 100°C for 1 to 10 hours is mentioned. In this case, the amount of alkali metal hydroxide used is in the range of 0.8 to 2.0 mol, preferably 0.9 to 1.5 mol, per 1 mol of hydroxyl group in the phenolic compound. . Epichlorohydrin is used in an excess amount relative to the hydroxyl groups in the phenolic compound, and is usually 1.5 to 15 moles per mole of hydroxyl groups in the phenolic compound. After the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain the desired epoxy. Resin can be obtained.

The purity of the epoxy resin, especially the amount of hydrolyzable chlorine, is preferably as low as possible from the viewpoint of improving the reliability of electronic components to which it is applied. Although not particularly limited, it is preferably 1000 ppm or less, more preferably 500 ppm or less. Note that the term "hydrolyzable chlorine" used in the first embodiment of the present invention refers to a value measured by the following method. That is, after dissolving 0.5 g of the sample in 30 ml of dioxane, adding 10 ml of 1N-KOH and boiling and refluxing for 30 minutes, cooling to room temperature, further adding 100 ml of 80% acetone water, and increasing the potential with a 0.002N-AgNO ₃ aqueous solution. This is the value obtained by titration.

As the curing agent used in the epoxy resin composition according to the first embodiment of the present invention, all those generally known as curing agents for epoxy resins can be used, including dicyandiamide, acid anhydrides, polyhydric phenols, These include aromatic and aliphatic amines. Among these, it is preferable to use polyhydric phenols as a curing agent in fields where high electrical insulation is required, such as semiconductor sealing materials. Specific examples of the curing agent are shown below.

Examples of polyhydric phenols include bihydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalene diol; , tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, etc. There are phenols. Furthermore, divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, naphthalenediol, There are polyhydric phenolic compounds synthesized using condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and p-xylylene glycol.

Examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, dodecynylsuccinic anhydride, nadic anhydride, Examples include trimellitic anhydride.

Examples of the amine curing agent include aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine; Aliphatic amines include ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

In the above epoxy resin composition, one type or a mixture of two or more of these curing agents can be used.

The compounding ratio of the epoxy resin and the curing agent is preferably such that the equivalent ratio of the epoxy group to the functional group in the curing agent is in the range of 0.8 to 1.5. Outside this range, unreacted epoxy groups or functional groups in the curing agent may remain even after curing, resulting in a decrease in the reliability of the sealing function.

The epoxy resin composition according to the first embodiment of the present invention contains an oligomer or polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, or phenoxy resin. Other modifiers and the like may be added as appropriate. The amount added is usually in the range of 1 to 30 parts by weight based on 100 parts by weight of the total resin components.

The epoxy resin composition according to the first embodiment of the present invention includes an inorganic filler other than the above-mentioned layered clay minerals such as mica and talc, a pigment, a retardant agent, a thixotropy imparting agent, a coupling agent, and a fluidity agent. Additives such as improvers can be added. Examples of inorganic fillers include spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, calcium carbonate, alumina, hydrated alumina, etc., and are used in semiconductor sealing materials. In this case, the preferred amount is 70% by weight or more, more preferably 80% by weight or more. When used in a heat dissipation substrate, the preferred blending amount is 20 to 90% by weight, more preferably 40 to 60% by weight, since fluidity is required.

Pigments include organic or inorganic extender pigments, scaly pigments, and the like. Examples of the thixotropy imparting agent include silicone-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, organic bentonite-based, and the like.

A curing accelerator can be used in the epoxy resin composition according to the first embodiment of the present invention, if necessary. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc. Specifically, 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphonium/tetraphenylborate, tetraphenylphosphonium/ethyltriphenylborate, tetra Examples include tetra-substituted phosphonium and tetra-substituted borates such as butylphosphonium and tetrabutylborate, tetraphenylboron salts such as 2-ethyl-4-methylimidazole and tetraphenylborate, and N-methylmorpholine and tetraphenylborate. The amount added is usually in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total resin components.

Furthermore, if necessary, the epoxy resin composition according to the first embodiment of the present invention may contain a mold release agent such as carnauba wax or OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, and carbon. Coloring agents such as black, flame retardants such as antimony trioxide, stress reducing agents such as silicone oil, lubricants such as calcium stearate, etc. can be used.

The epoxy resin composition according to the first embodiment of the present invention is made into a varnish state in which an organic solvent is dissolved, and then impregnated into a fibrous material such as a glass cloth, an aramid nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, etc. By removing the solvent, it can be made into a prepreg. Further, in some cases, it can be applied to a sheet-like material such as copper foil, stainless steel foil, polyimide film, polyester film, etc. to form a laminate.

By heating and curing the epoxy resin composition according to the first embodiment of the present invention, a cured resin product according to the first embodiment of the present invention can be obtained. This cured product can be obtained by molding an epoxy resin composition by methods such as casting, compression molding, and transfer molding. The temperature at this time is usually in the range of 120 to 220°C. Furthermore, a molded article having a crystallinity of 10% or more has high thermal conductivity and is suitable for high thermal conductive applications such as heat dissipation substrates. In addition, the degree of crystallinity is affected by the temperature control during molding, and if molded at a high temperature exceeding 200°C, it will become amorphous, making it difficult to obtain a molded product with an observable crystallinity, so it is necessary to heat it in stages. It is preferable. More preferably, the molding is performed by heating stepwise at a temperature in the range of 120 to 200° C. for a period of 30 seconds to 1 hour (preferably 1 minute to 30 minutes). Further, after molding, post-curing may be performed to adjust the degree of crystallinity as described above. The temperature of post-cure is 130°C to 250°C, and the time is in the range of 1 hour to 24 hours, but the endothermic peak temperature measured with the differential scanning calorimeter and conditions as shown in the example is It is desirable to perform post-curing at a temperature 5°C to 40°C lower for 1 to 24 hours. The degree of crystallinity of the molded product (cured product) can be determined based on the ratio of the crystallinity peak by the method described in Examples.

<Second embodiment>
The second embodiment of the present invention will be described in detail below.

The second embodiment of the present invention relates to a vinyl resin composition using vinyl resin as the crystalline resin. In this second embodiment, the vinyl resin used in the vinyl resin composition is one that is crystalline at room temperature, and has a melting point of more than 80°C and less than 200°C, as described above. Preferably, the melting point range is 90-200°C, more preferably 110-180°C. As mentioned above, the melting point is the endothermic peak temperature accompanying the melting of the crystal in scanning differential thermal analysis. Vinyl resins with melting points higher than 200°C have strong crystallinity and tend to reduce solvent solubility and melt-kneading properties, while cured products using vinyl resins with melting points lower than 90°C do not improve thermal conductivity. Tend.

The vinyl resin used in the second embodiment of the present invention preferably has a vinyl equivalent weight in the range of 150 to 1000 g/eq. More preferably, it is in the range of 200 to 500 g/eq. If it is larger than this range, the reactivity tends to be low, and some components become unreacted during curing, which tends to lower heat resistance and reliability. When it is smaller than this range, solvent solubility and melt-kneading properties tend to decrease, the cured product becomes hard and brittle, and film properties tend to decrease.

Regarding polar groups, the vinyl resin used in the second embodiment of the present invention preferably has a hydroxyl equivalent of 5000 g/eq or more, and preferably has a total chlorine amount of 2000 ppm or less.

The vinyl resin used in the second embodiment of the present invention can be obtained by reacting the hydroxyl group of a hydroxy resin with an aromatic vinylating agent such as chloromethylstyrene; When the hydroxyl resin has many hydroxyl groups and the hydroxyl equivalent is less than 5000 g/eq, curing tends to be insufficient and thermal conductivity and heat resistance tend to decrease. Moreover, since the hydroxyl group is a polar group, its remaining tends to inhibit the reduction of the dielectric constant and dielectric loss tangent. The hydroxyl equivalent is more preferably 8,000 g/eq or more, still more preferably 10,000 g/eq or more.

On the other hand, the chlorine component comes from chloromethylstyrene and from the crosslinking agent in the raw material for producing hydroxy resin. These are difficult to remove if the vinyl resin has low solvent solubility. When more than 2000 ppm of chlorine components remain, there is a tendency for the reduction of dielectric constant and dielectric loss tangent to be inhibited, and the curing reaction to be inhibited, thereby decreasing thermal conductivity and heat resistance. The total amount of chlorine is more preferably 1000 ppm or less, still more preferably 800 ppm or less.

The vinyl resin used in the second embodiment of the present invention can be suitably obtained by reacting a hydroxy resin (hydroxy compound) with an aromatic vinylating agent. Although not limited to, for example, vinyl resins having structures represented by the following formulas (2-1) to (2-3) can be preferably mentioned. The structures of formulas (2-1) to (2-3) below are structural skeletons that can be expected to have thermal conductivity that can suppress intramolecular and intermolecular molecular mobility, and have good solvent solubility and melt-kneading properties. It is a preferred embodiment as a resin that achieves the object of the present invention because it has good properties and can be molded into a uniform cured product and exhibits thermal conductivity.

<Vinyl resin of formula (2-1)>
A vinyl resin represented by the above formula (2-1) can be obtained by reacting a hydroxy resin (hydroxy compound) represented by the general formula (2-4) with chloromethylstyrene. This reaction can be carried out in the same manner as the well-known vinylation reaction.

R ¹ to R ⁶ in formula (2-4) are the same as in formula (2-1).

In formulas (2-1) and (2-4), R ¹ to R ⁶ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. Alkyl groups are preferred from the viewpoint of solvent solubility, and aromatic groups are preferred from the viewpoints of heat resistance and high thermal conductivity. In the case of an alkyl group having a carbon number larger than 6, it becomes difficult to suppress molecular movement, and there is also a concern that compatibility may decrease. In addition, a bulky structure with large steric hindrance may cause a decrease in solvent solubility due to increased crystallinity. A more preferred structure is a methyl group or a phenyl group. In formulas (2-1) and (2-4), R ¹ to R ⁶ may be a mixture of different structures.

The substitution position of the vinyl benzyl ether in the vinyl resin of formula (2-1) is not particularly limited, but from the viewpoint of thermal conductivity and heat resistance, it is preferably the para position with respect to the methine group connecting the three aromatic rings. preferable. In particular, it is more preferable that all three vinyl benzyl ethers are at the para position.

The number average molecular weight (Mn) of the vinyl resin of formula (2-1) is preferably 2000 or less, more preferably 1500 or less. It may also contain a multibranched product represented by the following general formula (2-5). t in formula (2-5) is the number of repetitions (number average) and represents a number from 0 to 20. Preferably, it is a mixture of components having different values of t. From the viewpoint of thermal conductivity, the content of t=0 bodies is preferably 50% by weight (wt%) or more, and more preferably 80wt% or more.

The trifunctional hydroxy compound of formula (2-4) preferably has a hydroxyl equivalent of 90 to 350 g/eq, more preferably 100 to 200 g/eq. The trifunctional hydroxy compound of formula (2-4) can be produced by a general method, for example, by polycondensing a monovalent phenol compound and an aromatic aldehyde.

Examples of monovalent phenol compounds include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, p-t-butylphenol, - Monoalkylphenols such as cyclohexylphenol, m-cyclohexylphenol, and p-cyclohexylphenol; dialkylphenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, and 2,6-xylenol ; Trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol, furthermore, 2-phenylphenol, 4-phenylphenol, 3-benzyl-1,1'-biphenyl-2-ol, Examples include hydroxybiphenyls such as 3-benzyl-1,1'-biphenyl-4-ol, 3-phenylphenol, and 2,6-diphenylphenol. In terms of solvent solubility, reactivity, and feedability, 2,5-xylenol, 2,6-xylenol, and 2-phenylphenol are particularly preferred. These phenol compounds can be used alone or in combination of two or more.

Examples of aromatic aldehydes include 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 4-hydroxy-2,5 -dimethylbenzaldehyde, 3,5-diethyl-4-hydroxybenzaldehyde, and other hydroxybenzaldehydes. From the viewpoint of heat resistance and thermal conductivity, 4-hydroxybenzaldehyde is preferred.

The polycondensation of a phenol compound and an aromatic aldehyde may be carried out using an acid catalyst, such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, and the like. These acid catalysts can be used alone or in combination of two or more. Moreover, among these acid catalysts, sulfuric acid and para-toluenesulfonic acid are preferable because of their excellent activity. Note that the acid catalyst may be added before or during the reaction.

The polycondensation of a phenol compound and an aromatic aldehyde may be performed in the presence of a solvent to obtain a polycondensate, if necessary. Examples of the solvent include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 - Polyols such as hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene Glycol ethers such as glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, ethylene glycol monophenyl ether; 1,3-dioxane, 1, Examples include cyclic ethers such as 4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These solvents can be used alone or in combination of two or more. Furthermore, among these solvents, 2-ethoxyethanol is preferred from the viewpoint of excellent solubility of the resulting compound.

The reaction temperature during polycondensation of the phenol compound and aromatic aldehyde is preferably in the range of 20 to 140°C, more preferably in the range of 80 to 110°C.

The charging ratio of phenol compound/aromatic aldehyde is preferably in the range of 1/0.1 to 1/0.5 in terms of molar ratio, since the phenol compound after the reaction can be easily removed by reprecipitation, etc. It is preferably in the range of 1/0.3 to 1/0.5.

The vinyl resin of formula (2-1) can be suitably obtained by reacting a trifunctional hydroxy compound with an aromatic vinylating agent. For example, but not limited to, a vinyl resin suitable for the present invention represented by the above formula (2-1) can be obtained by reacting a trifunctional hydroxy compound represented by the above formula (2-4) with chloromethylstyrene. be able to. This reaction can be carried out in the same manner as the well-known vinylation reaction.

The blending ratio is preferably 0.8 to 1.2 equivalents of the aromatic vinylating agent (for example, chloromethylstyrene) to 1.0 equivalents of hydroxyl groups, which are the functional groups of the trifunctional hydroxy compound. However, if the reactivity of the trifunctional hydroxy compound is low, an excess amount of the aromatic vinylating agent may be added and removed after the reaction.

As the aromatic vinylating agent, halomethylstyrene, especially chloromethylstyrene is preferred. Other examples include bromomethylstyrene, its isomers, and those with substituents. Regarding the substitution position of the halomethyl compound, for example, in the case of halomethylstyrene, the 4-position is preferable, and the 4-position preferably accounts for 60% by weight or more of the total.

The reaction between the trifunctional hydroxy compound and the aromatic vinylating agent can be carried out without a solvent or in the presence of a solvent. The reaction can be carried out by adding an aromatic vinylating agent to the hydroxy compound, adding a metal hydroxide to carry out the reaction, and removing the generated metal salt by a method such as filtration or washing with water. Examples of the solvent include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, and cyclohexanone. From the viewpoint of reactivity, methyl ethyl ketone is preferred. Specific examples of metal hydroxide include sodium hydroxide, potassium hydroxide, etc., but are not limited thereto.

The temperature of the vinylation reaction is preferably 90°C or lower, more preferably 70°C or lower. If the temperature is higher than this, heat-induced self-polymerization of the vinylbenzyl ether group may proceed, making it difficult to control the reaction. In order to suppress self-polymerization, polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso, nitrone compounds, and oxygen may be used.

The end point of the reaction can be determined by tracking the remaining amount of halomethylstyrene as an aromatic vinylating agent using various chromatograms such as GPC, and the reaction rate can be determined depending on the type and amount of metal hydroxide, addition rate, solid It can be adjusted by adjusting the concentration etc.

<Vinyl resin of formula (2-2), vinyl resin of formula (2-3)>
As the vinyl resin used in the second embodiment of the present invention, in addition to the vinyl resin represented by formula (2-1), those represented by formulas (2-2) and (2-3) are also suitable. These vinyl resins may be used in combination, and it is preferable that the vinyl resins represented by formulas (2-1) to (2-3) contain 50 wt% or more of the entire resin component. More preferably, it is 70 wt% or more. If the proportion used is less than this, the effect of improving heat resistance, thermal conductivity, etc. in a cured product may be small.

[Vinyl resin of formula (2-2)]
In the above formula (2-2), n is the number of repetitions (number average) and represents a number from 0 to 20. Usually, it is a mixture of components having different repeating number (n) values, and the average value (number average) of n is preferably in the range of 0.1 to 15, more preferably in the range of 0.5 to 10. .
A independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, or a divalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a benzene ring. , represents a naphthalene ring or a biphenyl ring. From the viewpoint of thermal conductivity, A is preferably a single bond, and X is preferably a biphenyl ring. It is desirable that the substitution positions of the two vinylbenzyl ether groups bonded to the biphenyl structure having A include at least a 2,2' form. In formula (2-2), when A is a single bond, that is, both ends are biphenyl rings, the substitution positions of the two bonded vinylbenzyl ether groups are the 4,4' position and the 2,2' position. is preferable, and the ratio of biphenyl at both terminals is preferably 40 to 90 mol% of the total at the 2,2' position. When A is other than a single bond, that is, when both ends of the vinyl resin are other than biphenyl rings, for example, a diphenylmethane structure, the substitution positions of the two bonded vinyl benzyl ether groups are such that the 4,4' position is 30 to 100 mol%. preferable.

The vinyl resin of formula (2-2) is preferably a polyfunctional vinyl resin represented by formula (2-6) below.

e and f in formula (2-6) are the number of repetitions (number average) and represent a number from 0 to 20. Preferably, it is a mixture of components having different values of e and f. The ratio (molar ratio) of e/(e+f) is preferably 0.50 to 0.95, more preferably 0.70 to 0.95. When it is less than 0.50, the effect of heat resistance and high thermal conductivity tends to be small, and when it is more than 0.95, crystallinity tends to become strong and solvent solubility tends to decrease. The average value of e is preferably 0.1 to 10, more preferably 0.5 to 5. The average value of f is preferably 0.1 to 5, more preferably 0.1 to 2.
Regarding A, it is the same as the above-mentioned formula (2-2).

The polyfunctional vinyl resin represented by the above formula (2-6) can be produced by reacting the polyhydric hydroxy resin represented by the formula (2-7) with chloromethylstyrene.

In the polyvalent hydroxy resin of formula (2-7), the ratios of A, e, f, and e/(e+f) are the same as in the polyfunctional vinyl resin of formula (2-6) above. The polyhydric hydroxy resin represented by formula (2-6) preferably has a hydroxyl equivalent of 100 to 350 g/eq. When these hydroxyl groups are partially or completely vinylated, a polyfunctional vinyl resin represented by formula (2-6) is obtained.

This polyhydric hydroxy resin of formula (2-7) is not limited, but for example, as shown in formula (2-11) below, 4,4'-dihydroxybiphenyl represented by formula (2-8) and formula ( It can be produced by reacting with an aromatic crosslinking agent having a biphenyl structure represented by formula (2-9) and then reacting with a bifunctional phenol compound represented by formula (2-10).

Here, Z in formula (2-9) represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms.

Here, A represents a single bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, or a divalent hydrocarbon group having 1 to 6 carbon atoms.

The molar ratio of the synthesis raw materials 4,4'-dihydroxybiphenyl represented by formula (2-8) and the bifunctional phenol compound represented by formula (2-10) is 4,4'-dihydroxy Biphenyl is preferably 0.50 to 0.95, more preferably 0.70 to 0.95. If the ratio of 4,4'-dihydroxybiphenyl is less than this range, heat resistance and high thermal conductivity tend to be insufficient, and if it is higher, the solvent solubility tends to decrease due to strong crystallinity.
Specifically, the difunctional phenol compound of formula (2-10) includes 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxy diphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, dihydroxydiphenylmethanes, 2,2-bis(4-hydroxyphenyl)propane, and especially 2,2'-dihydroxybiphenyl, 4,4 from the viewpoint of solvent solubility. '-dihydroxydiphenyl ether and dihydroxydiphenylmethane are preferred. The dihydroxydiphenylmethane may be a mixture of ortho, meta, and para, but preferably has an isomer ratio of 4,4'-dihydroxydiphenylmethane of 40% or less. If there is a large amount of 4,4'-dihydroxydiphenylmethane, the crystallinity will be strong and there is a concern that the solvent solubility will decrease.

In the aromatic crosslinking agent represented by the above formula (2-9), Z represents a hydroxyl group, a halogen atom, or an alkoxy group having 1 to 6 carbon atoms. Specific examples of the aromatic crosslinking agent include 4,4'-bishydroxymethylbiphenyl, 4,4'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, and 4,4'-bismethoxymethylbiphenyl. , 4,4'-bisethoxymethylbiphenyl. From the viewpoint of reactivity, 4,4'-bishydroxymethylbiphenyl or 4,4'-bischloromethylbiphenyl is preferable, and from the viewpoint of reducing ionic impurities, 4,4'-bishydroxymethylbiphenyl, Or 4,4'-bismethoxymethylbiphenyl is preferred.

The molar ratio when reacting a phenol and an aromatic crosslinking agent as shown in formula (2-11) is generally 0.2 to 0.00% of the aromatic crosslinking agent per mole of the phenol. The amount is in the range of 7 mol, more preferably in the range of 0.4 to 0.7 mol. When the amount is less than 0.2 mol, the proportion of n=0 of the polyhydric hydroxy resin represented by the formula (2-2) obtained becomes high, especially the 4,4'- represented by the formula (2-8). If there is a large amount of dihydroxybiphenyl, there is a concern that the solubility may decrease, such as exhibiting crystallinity. On the other hand, if the amount is more than 0.7 mol, the amount of high molecular weight components increases, and stable production may become difficult.

The reaction between the phenols and the aromatic crosslinking agent can be carried out without a catalyst or in the presence of an acid catalyst such as an inorganic acid or an organic acid. When using 4,4'-bischloromethylbiphenyl, the reaction can be carried out without a catalyst, but in general, it is necessary to suppress side reactions such as the formation of ether bonds due to the reaction of chloromethyl groups and hydroxyl groups. It is preferable to carry out the reaction in the presence of an acidic catalyst. This acidic catalyst can be appropriately selected from well-known inorganic acids and organic acids, such as mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and metasulfonic acid. Examples include organic acids such as acids, trifluorometasulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride, and solid acids.

As a solvent during the reaction, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc. Among these, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, etc. are particularly preferred. After completion of the reaction, the solvent may be removed from the obtained polyhydric hydroxy resin by distillation under reduced pressure, washing with water, reprecipitation in a poor solvent, etc., but the resin may be used as a raw material for the vinylation reaction with the solvent remaining. May be used.

The vinyl resin of formula (2-2), preferably the polyfunctional vinyl resin represented by formula (2-6), can be suitably obtained by reacting a polyhydric hydroxy resin with an aromatic vinylizing agent. can. For example, a polyfunctional vinyl resin represented by the above formula (2-6) can be obtained by reacting a polyhydric hydroxy resin represented by the above formula (2-7) with chloromethylstyrene. This reaction can be carried out in the same manner as the well-known vinylation reaction.
Note that the blending ratio, type of aromatic vinylating agent, reaction conditions, confirmation of the reaction end point, etc. can be the same as in the case of obtaining the vinyl resin of formula (2-1) above.

[Vinyl resin of formula (2-3)]
In the above formula (2-3), Y independently represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ - or -C (CH ₃ ) ₂ - is shown. B independently represents a benzonitrile structure or -(CH ₂ ) _q -, and preferably contains a benzonitrile structure in at least one molecule. More preferably, at least one molecule has both a benzonitrile structure and a -(CH ₂ ) _q - structure. q represents a number from 3 to 10. In terms of high thermal conductivity, Y is preferably a biphenyl structure that is a direct bond, -SO ₂ -, -CO-, -COO-, or -CONH-, and more preferably a biphenyl structure that is a direct bond, among which 4, A biphenyl structure at the 4' position is particularly preferred. On the other hand, in terms of moldability and solvent solubility, oxygen atoms, sulfur atoms, -CH ₂ -, and -C(CH ₃ ) ₂ - are preferred. The vinyl resin of formula (2-3) can be made into a mixture with each Y having a different structure, as shown in "independently", and the high thermal conductivity, moldability, and solvent solubility can be adjusted. is possible. p is the number of repetitions and represents a number from 0 to 15. Preferably, the number is 1 to 15. Preferably, it is a mixture of components having different values of p. The p value (average value) is preferably 1.0 to 3.0, more preferably 1.5 to 2.5.

The vinyl resin of formula (2-3) may be a mixture with a compound where p = 0, and the area % measured by gel permeation chromatography (GPC area %) is preferably 40% or less of p = 0. . More preferably, it is 35% or less. When the content of p=0 is more than 40%, the crystallinity is strong, the melting point exceeds 200° C., and the solvent solubility tends to decrease. Furthermore, those with p greater than 15 have low reactivity, and if unreacted components are produced during curing, heat resistance tends to decrease.

B represents a benzonitrile structure or an alkyl structure represented by -(CH ₂ ) _q -. Preferably, at least one molecule contains a benzonitrile structure, and more preferably at least one molecule contains both a benzonitrile structure and an alkyl structure represented by -(CH ₂ ) _q -. In other words, as B is also said to be "independently", the vinyl resin of formula (2-3) can be a mixture of B with different structures, and has high thermal conductivity, moldability, and solvent solubility. It is possible to adjust. B preferably contains a benzonitrile structure in an amount of 50 mol% or more, more preferably 70 mol% or more. The ratio of the benzonitrile structure to the alkyl structure is preferably less than 50 mol%, more preferably 10 mol% to 40 mol%, based on the mass of the raw material compound. When the alkyl structure is more than 50 mol %, the thermal conductivity and heat resistance of the cured product tend to decrease, and when it does not contain an alkyl structure, the crystallinity tends to become strong and the solvent solubility tends to decrease.

Regarding the alkyl structure represented by -(CH ₂ ) _q -, q is the repeating number and represents a number from 3 to 10. More preferably, the number is 4 to 8. If it is smaller than 3, flexibility tends to be low and the effect of relaxing crystallinity tends to be low. When it is larger than 10, the thermal conductivity and heat resistance of the cured product tend to decrease significantly.

Specifically, a vinyl resin represented by the following formula (2-12) can be preferably exemplified.

(However, g and h each independently represent a number from 1 to 15, and q represents a number from 3 to 10.)

The vinyl resin of formula (2-3) can be suitably obtained by reacting a hydroxy resin with an aromatic vinylating agent. For example, the vinyl resin of the present invention represented by the above formula (2-3) can be obtained by reacting a hydroxy resin represented by the general formula (2-13) with chloromethylstyrene. This reaction can be carried out in the same manner as the well-known vinylation reaction.
Note that the blending ratio, type of aromatic vinylating agent, reaction conditions, confirmation of the reaction end point, etc. can be the same as in the case of obtaining the vinyl resin of formula (2-1) above.

(However, Y independently represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂ -, -CO-, -COO-, -CONH-, -CH ₂ - or -C(CH ₃ ) ₂ - B independently represents a benzonitrile structure or -(CH ₂ ) _q -, and preferably at least one contains a benzonitrile structure. More preferably, at least one molecule contains a benzonitrile structure and -( (CH ₂ ) _q includes both structures of the alkyl structure represented by -. p and q each independently represent a number from 0 to 15, and q represents a number from 3 to 10.)

The hydroxy resin represented by formula (2-13) (including the case where it is a mixture with a compound where p=0) has a hydroxyl equivalent (g/eq) of preferably 150 to 300, more preferably 200 to 270. It is. The number average molecular weight (Mn) is preferably 350 to 800, more preferably 450 to 600.
p has the same meaning as p in the vinyl resin of formula (2-3), is the repeating number, and represents a number from 0 to 15. Preferably, the number is 1 to 15. Preferably, it is a mixture of components having different values of p. The p value (average value) is preferably 1.0 to 3.0, more preferably 1.5 to 2.5.

The hydroxy resin (phenolic compound) represented by formula (2-13) is not limited in its production method as long as it has a predetermined structure, but it can be produced by combining either or both of a benzonitrile compound and a dihalogen alkyl compound with a Y group. It can be suitably obtained by reacting a dihydroxy compound having the following in the presence of a basic catalyst.
In this case, examples of the benzonitrile compound include 2,4-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,6-dichlorobenzonitrile, 3,5-dichlorobenzonitrile, and 2,4-dibromobenzonitrile. , 2,5-dibromobenzonitrile, 2,6-dibromobenzonitrile, 3,5-dibromobenzonitrile, etc., and examples of the dihalogen alkyl compound include 1,3-dibromopropane, 1,4-dibromobutane. , 1,5-dibromopentane, 1,6-dibromohexane, etc., and examples of dihydroxy compounds having a Y group include 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4' -dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybenzophenone, bisphenol A, bisphenol F, and the like.
Regarding the method for producing a hydroxy resin (phenolic compound), for more detailed specific conditions, refer to, for example, WO2021/201046.

Although the vinyl resin used in the second embodiment of the present invention can be cured alone, a vinyl resin composition containing various other additives in addition to the above-mentioned layered clay minerals such as talc and mica may be used. It is also suitable to use it as As one of the other additives, in particular, a radical polymerization initiator such as an azo compound or an organic peroxide can be added to accelerate curing. The radical polymerization initiator may be blended in an amount of, for example, 0.01 to 10 parts by weight per 100 parts by weight of the vinyl resin.

The vinyl resin composition according to the second embodiment of the present invention has a vinyl resin and a layered clay mineral as an additive as essential components, but other vinyl compounds and other thermosetting resins can be blended, Examples include epoxy resin, oxetane resin, maleimide resin, acrylate resin, polyester resin, polyurethane resin, polyphenylene ether resin, and benzoxazine resin.

In order to increase thermal conductivity, inorganic fillers other than the above-mentioned layered clay minerals, such as glass cloth, carbon fiber, alumina, and boron nitride, may be blended.

For the purpose of imparting higher thermal conductivity, the higher the thermal conductivity of the inorganic filler, the more preferable it is. Preferably it is 20 W/m·K or more, more preferably 30 W/m·K or more, and still more preferably 50 W/m·K or more. At least a portion of the inorganic filler, preferably 50 wt% or more, has a thermal conductivity of 20 W/m·K or more. The average thermal conductivity of the inorganic filler as a whole increases in the order of 20 W/m·K or more, 30 W/m·K or more, and 50 W/m·K or more.

Examples of inorganic fillers having such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide. It will be done. The content of the inorganic filler in the vinyl resin composition according to the second embodiment of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more when used in a semiconductor encapsulant. be. When used in a heat dissipation substrate, the preferred blending amount is 20 to 90% by weight, more preferably 40 to 60% by weight, since fluidity is required.

In order to improve adhesive strength and improve handling of the composition, various other additives include, for example, silane coupling agents, antifoaming agents, internal mold release agents, and flow control agents. Additionally, various known additives such as colorants, flame retardants, thixotropy imparting agents, etc. can be used within the scope of the present invention.

The vinyl resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, and used as a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper. It is also possible to obtain a cured product by hot press molding a prepreg obtained by impregnating a material and drying it by heating.

In addition, in some cases, a laminate can be obtained by applying the vinyl resin composition according to the second embodiment of the present invention on a sheet-like material such as copper foil, stainless steel foil, polyimide film, polyester film, etc. A cured product can also be obtained by hot press molding a resin sheet obtained by heating and drying.

The vinyl resin composition according to the second embodiment of the present invention is suitable for providing a cured product with high thermal conductivity, that is, providing a cured product for high thermal conductivity. Here, when the cured product of the vinyl resin composition according to the second embodiment of the present invention contains an inorganic filler, the thermal conductivity is preferably 8 W/m·K or more, and 10 W/m·K or more. is more preferable. When the inorganic filler is not contained, it is preferably 0.25 W/m·K or more, more preferably 0.30 W/m·K or more.

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. However, the present invention is not limited to these. Unless otherwise specified, "parts" represent parts by weight, and "%" represent % by weight.

<Example according to the first embodiment>
Hereinafter, the first embodiment of the present invention will be described in more detail with reference to Examples.

Synthesis Example 1-1 (Production of epoxy resin A)
100.0 g of 4,4'-dihydroxydiphenyl ether was dissolved in 460 g of epichlorohydrin and 70 g of diethylene glycol dimethyl ether, and 90.8 g of a 48% aqueous sodium hydroxide solution was added dropwise at 60° C. and under reduced pressure (approximately 130 Torr) over 3 hours. During this time, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropwise addition was completed, the reaction was continued for another 1 hour, and after dehydration, epichlorohydrin was distilled off, 580 g of toluene was added, and the salt was removed by washing with water. Thereafter, water was removed by liquid separation, and toluene was distilled off under reduced pressure to obtain 126 g of a white crystalline epoxy resin (epoxy resin A). The epoxy equivalent was 163, the hydrolyzable chlorine was 150 ppm, the melting point was 83°C, and the viscosity at 150°C was 10 mPa·s. The n=0 (monomer) of the epoxy resin obtained from 4,4'-dihydroxydiphenyl ether was determined by GPC measurement to be 91.2%. The percentage of n=1 or more was 8.8%.

Synthesis Example 1-2 (Production of epoxy resin B)
50.0 g of hydroquinone and 100.0 g of 4,4'-dihydroxybiphenyl were dissolved in 1000 g of epichlorohydrin and 150 g of diethylene glycol dimethyl ether, and 16.5 g of 48% sodium hydroxide was added at 60° C. and stirred for 1 hour. Thereafter, 148.8 g of a 48% aqueous sodium hydroxide solution was added dropwise under reduced pressure (approximately 130 Torr) over 3 hours. During this time, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropwise addition was completed, the reaction was continued for another 1 hour, and after dehydration, epichlorohydrin was distilled off, 600 g of methyl isobutyl ketone was added, and the salt was removed by washing with water. Thereafter, 13.5 g of 48% sodium hydroxide was added at 85° C., stirred for 1 hour, and washed with 200 mL of warm water. Thereafter, after water was removed by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 224 g of a white crystalline epoxy resin (epoxy resin B). The epoxy equivalent was 139, the hydrolyzable chlorine was 320 ppm, the melting point was 125°C, and the viscosity at 150°C was 3.4 mPa·s. The n=0 (monomer) of the epoxy resin obtained from 4,4'-dihydroxybiphenyl determined by GPC measurement was 67.2%. In addition, n=0 (monomer) of the epoxy resin obtained from hydroquinone is . It was 23.1%. The percentage of n=1 or more was 9.7%.

Synthesis Example 1-3 (Production of epoxy resin C)
After dissolving 115.7 g of 4,4'-dihydroxybiphenyl in 700 g of NMP in a 2 L 4-neck separable flask, 56.7 g of potassium carbonate was added, and the temperature was raised to 120° C. with stirring under a nitrogen stream. Thereafter, 35.6 g of 2,6-dichlorobenzonitrile was added, the temperature was raised to 145°C, and the mixture was reacted for 6 hours. After neutralizing the reaction solution by adding 49.2 g of acetic acid, NMP was distilled off under reduced pressure. After adding 500 mL of MIBK to the reaction solution and dissolving the product, the formed salt was removed by washing with water. Thereafter, MIBK was removed by vacuum distillation to obtain 129 g of hydroxy resin. The hydroxyl equivalent of the obtained hydroxy resin was 170 g/eq. , the melting point was 272°C. 50.0 g of the obtained hydroxy resin, 380 g of epichlorohydrin, and 96 g of diethylene glycol dimethyl ether (diglyme) were charged, and 27.5 g of a 48.6% aqueous sodium hydroxide solution was added dropwise at 65° C. under reduced pressure (approximately 130 Torr) over 3 hours. . During this time, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropwise addition was completed, the reaction was continued for another 1 hour for dehydration. Thereafter, epichlorohydrin and diglyme were distilled off under reduced pressure, dissolved in 200 mL of methyl isobutyl ketone, and the generated salt was removed by filtration. Thereafter, 0.4 g of a 48% aqueous sodium hydroxide solution was added, and the mixture was reacted at 80° C. for 2 hours. After the reaction, filtration and water washing were performed, and the solvent methyl isobutyl ketone was distilled off under reduced pressure to obtain 43 g of an epoxy resin that was solid at room temperature (epoxy resin C). The melting point of the obtained epoxy resin C was 139°C, and the epoxy equivalent was 226 g/eq. , hydrolyzable chlorine was 80 ppm.

Synthesis Example 1-4 (Production of epoxy resin D)
77.5 g of 4,4'-dihydroxybiphenyl, 119.3 g of diethylene glycol dimethyl ether, and 41.8 g of 4,4'-bischloromethylbiphenyl were placed in a 1,000 ml four-necked flask, and the mixture was heated at 160°C under a nitrogen stream with stirring. The temperature was raised to 100 mL, and the reaction was carried out for 20 hours to produce a polyhydric hydroxy resin with an OH equivalent of 135 g/eq. After the reaction was completed, 45.6 g of diethylene glycol dimethyl ether was collected, 455.1 g of epichlorohydrin was added, and 70.5 g of a 48% aqueous sodium hydroxide solution was added dropwise at 62° C. under reduced pressure (approximately 130 Torr) over 4 hours. During this time, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropwise addition was completed, the reaction was continued for an additional hour. After that, epichlorohydrin was distilled off, methyl isobutyl ketone was added, salt was removed by water washing, filtration and water washing were performed, and then methyl isobutyl ketone was distilled off under reduced pressure to obtain 129 g of epoxy resin (epoxy resin D). This epoxy resin D had an epoxy equivalent of 200 g/eq, a softening point of 125°C, a melting point of 120°C, a melt viscosity of 0.21 Pa·s, and a hydrolyzable chlorine content of 230 ppm.

Examples 1-1 to 1-9, Comparative Examples 1-1 to 1-5
The epoxy resins used include the epoxy resin obtained in Synthesis Example 1-1 (Epoxy Resin A), the epoxy resin obtained in Synthesis Example 1-2 (Epoxy Resin B), and the epoxy resin obtained in Synthesis Example 1-3 (Epoxy Resin C). ), the epoxy resin obtained in Synthesis Example 1-4 (epoxy resin D) was used. As a curing agent, 4,4'-dihydroxydiphenyl ether (curing agent A, OH equivalent 101 g/eq.), phenol novolac (curing agent B: manufactured by Aica Kogyo, BRG-557, OH equivalent 105 g/eq., softening triphenylphosphine as a curing accelerator, spherical alumina (manufactured by Denka, DAW-10, average particle size 12.2 μm) as an inorganic filler, and talc (additive A) as an additive. , average particle size 10-15 μm, Fuji Film Wako Pure Chemical Industries, Ltd.), mica (additive B, synthetic mica, Fuji Film Wako Pure Chemical Industries, Ltd.), additive C (1,3:2, 4-bis(3,4-dimethylbenzylidene)-D-sorbitol, manufactured by Tokyo Kasei Kogyo) or additive D (sodium 2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g][ 1,3,2]dioxaphosphosine-6-olate 6-oxide (manufactured by Tokyo Kasei Kogyo) was used.

The ingredients shown in Table 1 were blended, thoroughly mixed with a mixer, then kneaded with a heating roll for about 5 minutes, cooled, and pulverized for Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1, respectively. An epoxy resin composition No.-5 was obtained. After molding using this epoxy resin composition at 175°C for 5 minutes, post-curing was performed at 180°C for 12 hours to obtain a cured molded product, and its physical properties were evaluated. The results are summarized in Table 1. Note that the numbers for each component in Table 1 represent parts by weight.

[evaluation]
(1) Thermal conductivity The thermal conductivity was measured by an unsteady hot wire method using a NETZSCH model LFA447 thermal conductivity meter.
(2) Measurement of melting point and heat of fusion (DSC method)
Measurement was performed using a TG/DTA7300 differential scanning calorimeter manufactured by Hitachi High-Tech Science, using a precisely weighed sample of about 10 mg, under a nitrogen stream at a heating rate of 10° C./min. In addition, when a cured product containing an inorganic filler was used as a sample, the heat of fusion was converted only to the resin component.
(3) Coefficient of Linear Expansion, Glass Transition Temperature The coefficient of linear expansion and glass transition temperature were measured at a heating rate of 10° C./min using a thermomechanical measuring device TMA7100 manufactured by Hitachi High-Tech Science.
(4) Water absorption rate A disk with a diameter of 50 mm and a thickness of 3 mm was molded, and after post-curing, it was allowed to absorb moisture for 100 hours at 85° C. and a relative humidity of 85%. This was the weight change rate.
(5) XRD measurement and crystallinity calculation XRD measurement was performed using RINT TTR3 manufactured by Rigaku Corporation. The measurement conditions were as follows. Diffraction angle 2θ: 10° to 30°, scanning speed: 0.25°/min, divergence slit: 1/2 degree, divergence vertical restriction slit: 10 mm, scattering slit: 1/2 degree, light receiving slit: 0.3 mm.
The crystallinity was calculated by the following formula, excluding the talc diffraction peak observed in the 2θ range of 28° to 29°. When mica is used, the peak observed in the 6° to 8° region is excluded. Here, a crystalline peak is a sharp peak with a diffraction peak width of 5° or less, preferably 3° or less, and an amorphous peak is a broad peak with a diffraction peak width of 8° or more. It is the peak.
Crystallinity = [Crystalline peak area / (Crystalline peak area + Amorphous peak area)] * 100

As is clear from these results, the epoxy resin compositions obtained in Examples have excellent thermal conductivity and are therefore suitable for power devices and automotive applications. In addition, when using the epoxy resin composition according to the comparative example that does not contain the predetermined layered clay mineral, no crystalline peak was obtained but an amorphous peak, so the crystallinity was 0% in both cases. Ta.

[Effects of the invention and industrial applicability of the first embodiment]
The epoxy resin composition exemplified in the first embodiment can produce cured molded products with excellent moldability, reliability, high thermal conductivity, low water absorption, low thermal expansion, high heat resistance, and flame retardancy. It is suitably applied as an insulating material for electrical and electronic materials such as semiconductor encapsulation, laminates, and heat dissipation substrates, and exhibits excellent heat dissipation, high heat resistance, flame retardancy, and high dimensional stability. The reason why such a specific effect occurs is presumed to be that the layered clay mineral enhances the orientation of a specific cured epoxy resin having a rigid structure such as a biphenyl structure.

<Example according to the second embodiment>
Hereinafter, the second embodiment of the present invention will be described in more detail with reference to Examples.
In addition, the measurement methods were as follows.

1) OH equivalent (hydroxyl group equivalent)
Using a potentiometric titrator, use 1,4-dioxane as a solvent, perform acetylation with 1.5 mol/L acetyl chloride, decompose excess acetyl chloride with water, and use 0.5 mol/L-potassium hydroxide. and titrated.

2) Vinyl equivalent React the sample with Wiess solution (iodine monochloride solution), leave it in a dark place, then reduce excess iodine chloride to iodine, titrate the iodine content with sodium thiosulfate, and calculate the iodine value. did. The iodine value was converted into vinyl equivalent.

3) Total chlorine After dissolving 1.0 g of the sample in 25 ml of butyl carbitol, add 25 ml of 1N-KOH propylene glycol solution, heat under reflux for 10 minutes, cool to room temperature, and then add 100 ml of 80% acetone water to dissolve 0.002N. - Measured by potentiometric titration with an aqueous AgNO ₃ solution.

4) GPC measurement A main unit (HLC-8220GPC, manufactured by Tosoh Corporation) equipped with columns (4 TSKgel SuperMultipore HZ-N, manufactured by Tosoh Corporation) in series was used, and the column temperature was set at 40°C. Further, tetrahydrofuran (THF) was used as the eluent at a flow rate of 0.35 mL/min, and a differential refractive index detector was used as the detector. As a measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF, and 50 μL of the solution was filtered with a microfilter. For data processing, GPC-8020 Model II version 6.00 manufactured by Tosoh Corporation was used.

5) Melting point, heat of fusion (DSC method)
Using a differential scanning calorimeter DSC7020 model manufactured by Hitachi High-Tech Science Co., Ltd., measurement was performed using a precisely weighed sample of about 10 mg under a nitrogen stream at a heating rate of 10° C./min.

6) Solvent solubility (precipitation temperature)
After weighing 2 g of resin and 1 g of methyl ethyl ketone into a sample bottle and heating and dissolving them, the temperature was gradually lowered in a constant temperature bath, and the temperature in the bath where the resin precipitated was measured. The higher the precipitation temperature (°C), the worse the solvent solubility.

7) Glass transition point (Tg)
Tg was determined using a thermomechanical measuring device (EXSTAR TMA/7100, manufactured by Hitachi High-Tech Science Co., Ltd.) at a temperature increase rate of 10° C./min.

8) 5% weight loss temperature (Td5), residual carbon percentage Using a thermogravimetric/differential thermal analyzer (EXSTAR TG/DTA7300 manufactured by Hitachi High-Tech Science), under nitrogen atmosphere and at a heating rate of 10°C/min, The 5% weight loss temperature (Td5) was measured. In addition, the weight loss at 700°C was measured and calculated as the residual carbon percentage.

9) Thermal conductivity The thermal conductivity was measured by an unsteady hot wire method using a NETZSCH model LFA447 thermal conductivity meter.

10) Dielectric constant and dielectric loss tangent Measured according to JIS C 2138 standard. The measurement frequency is shown as a value of 1 GHz.

11) Electrodesorption ionization mass spectrometry (FD-MS)
Measurement was performed using a mass spectrometer JMS-T100GCV (manufactured by JEOL Ltd.). The sample was dissolved in acetone and subjected to measurement.

(Synthesis example 2-1)
In a 1000 mL 4-necked flask, 73.6 g (0.60 mol) of 2,5-xylenol (Structural Formula 2-14 below),

24.4 g (0.20 mol) of p-hydroxybenzaldehyde (Structural formula 2-15 below)

was charged and dissolved in 200.0 g of 2-ethoxyethanol. After adding 20.0 g of sulfuric acid while cooling in an ice bath, the mixture was heated and stirred at 100° C. for 3 hours to react. After the reaction, the resulting solution was reprecipitated with water, washed with water, filtered, and vacuum dried to obtain 65.0 g of a trifunctional hydroxy compound with a hydroxyl equivalent of 118 g/eq. The trifunctional hydroxy compound is a compound in formula (2-4) in which R ¹ to R ⁴ are all methyl groups and R ⁵ and R ⁶ are hydrogen atoms.
Next, 59.0 g (0.17 mol) of the obtained trifunctional hydroxy compound, 400 g of methyl ethyl ketone, and 91.6 g (0.60 mol) of chloromethylstyrene (Structural Formula 2-16 below) were placed in a 1000 ml four-necked flask.

was added, the temperature was raised to 60°C, 33.7 g of potassium hydroxide dissolved in 101 g of methanol was added dropwise over 3 hours, and the reaction was further continued for 6 hours. After the reaction was completed, it was filtered, the solvent was distilled off, reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 102.4 g of vinyl resin (vinyl resin A). The basic structure of vinyl resin A is that in formula (2-1), R ¹ to R ⁴ are all methyl groups, R ⁵ and R ⁶ are hydrogen, the vinyl equivalent is 225 g/eq, and the hydroxyl equivalent is 12000 g/eq. eq, total chlorine was 600 ppm, melting point was 130° C., and Mn was 780.
A GPC chart of the obtained vinyl resin A is shown in FIG.

(Synthesis example 2-2)
In a 1000 ml four-necked flask, 65.3 g (0.35 mol) of 4,4'-dihydroxybiphenyl (Structural Formula 2-17 below),

121.2 g of diethylene glycol dimethyl ether, 58.7 g (0.23 mol) of 4,4'-bis(chloromethyl)biphenyl (Structure 2-18 below)

was charged, the temperature was raised to 170°C with stirring under a nitrogen stream, and the reaction was carried out for 3 hours, and further dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane (Structure 2-19 below): 36.2%, 2,4 '-Dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%) 7.8g (0.04mol)

were reacted to produce a polyhydric hydroxy resin (hydroxyl equivalent: 129 g/eq) according to formula (2-7).
After the reaction, 50.7 g of diethylene glycol dimethyl ether was collected, 320 g of methyl ethyl ketone and 135.5 g of chloromethylstyrene were added, the temperature was raised to 60°C, and 49.8 g of potassium hydroxide dissolved in 150 g of methanol was added dropwise over 3 hours. , and reacted for an additional 6 hours. After the reaction is completed, it is filtered, the solvent is distilled off, reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain formula (2-6) (that is, formula (2-2)). 141 g of such a white solid vinyl resin was obtained (vinyl resin B). Vinyl resin B had a vinyl equivalent of 275 g/eq, a hydroxyl equivalent of 15000 g/eq, a total chlorine content of 300 ppm, an Mn of 1330, and a melting point of 145°C. The basic structure of the polyvalent hydroxy resin and vinyl resin B is that in formulas (2-6) and (2-7), A is a -CH ₂ - group, and the ratio (molar ratio) of e/(e+f) is 0. .93, e is 4.2, and f is 0.3.
A GPC chart of the obtained vinyl resin B is shown in FIG.

(Synthesis example 2-3)
74.5 g (0.4 mol) of 4,4'-dihydroxybiphenyl and 18.4 g (0.08 mol) of 1,5-dibromopentane (structural formula 2-20 below) were placed in a 2L 4-neck separable flask. ,

After dissolving in 500 g of N-methyl-2-pyrrolidone, 41.5 g of potassium carbonate was added, and the temperature was raised to 120° C. with stirring under a nitrogen stream. Then, 20.6 g (0.12 mol) of 2,6-dichlorobenzonitrile (Structural Formula 2-21 below)

was added, the temperature was raised to 145°C, and the mixture was reacted for 6 hours. After neutralizing the reaction solution by adding 28.2 g of acetic acid, N-methyl-2-pyrrolidone was distilled off under reduced pressure. After 250 mL of methyl isobutyl ketone was added to the reaction solution to dissolve the product, the formed salt was removed by washing with water. Thereafter, methyl isobutyl ketone was removed by vacuum distillation to obtain 72.6 g of hydroxy resin. The hydroxyl equivalent of the obtained hydroxy resin was 225 g/eq, and the Mn was 520. The p value (average value) was 2.3. The basic structure of the hydroxy resin is a structural unit when Y is a direct bond and B is a benzonitrile structure in formula (2-13), and a structure when -(CH ₂ ) _q - (q=5) It has both units.
Next, 74.3 g (0.33 mol) of the obtained hydroxy resin, 400 g of methyl ethyl ketone, and 61.0 g (0.40 mol) of chloromethylstyrene were added to a 1000 ml four-necked flask, and the temperature was raised to 60°C. 22.4 g (0.40 mol) of potassium hydroxide dissolved in 70 g was added dropwise over 3 hours, and the reaction was further continued for 6 hours. After the reaction is completed, it is filtered, the solvent is distilled off, reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain a product according to formula (2-12) (that is, formula (2-3)). 84.3 g of vinyl resin was obtained (vinyl resin C). Vinyl resin C had a vinyl equivalent of 341 g/eq, a hydroxyl equivalent of 10,000 g/eq, a total chlorine content of 900 ppm, an Mn of 710, and a melting point of 174°C. The basic structure of vinyl resin C is formula (2-12) and formula (2-3), where q is 5, g is 1 to 3, h is 1 to 3, and the p value (average value) is 1.8. Met.
The GPC chart of the obtained vinyl resin C is shown in FIG. 5, and the FD-MS spectrum is shown in FIG.

(Synthesis example 2-4)
A 1000 ml four-neck flask was charged with 40.8 g of 4,4'-bis(chloromethyl)biphenyl, 75.5 g of 4,4'-dihydroxybiphenyl, and 120 g of diethylene glycol dimethyl ether, and the temperature was raised to 160°C while stirring under a nitrogen stream. The mixture was heated and reacted for 10 hours. Next, the temperature was raised to 70°C, 280 g of diethylene glycol dimethyl ether and 129.5 g of chloromethylstyrene were added, and the reaction was carried out while dropping 100.0 g of 48% potassium hydroxide. Gas chromatography was performed to confirm that there was no residual chloromethylstyrene. After confirmation, the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, neutralized, and washed with water to obtain a vinyl resin (vinyl resin D). The vinyl equivalent of the obtained vinyl resin D was 256 g/eq, the hydroxyl equivalent was 1500 g/eq, the total chlorine was 1270 ppm, the Mn was 1100, and the melting point was 210°C.
The reason why vinyl resin D has a relatively high melting point is inferred as follows. That is, since dihydroxydiphenylmethane is not used as a raw material, the melting point of the resulting hydroxy resin is lower than that in Synthesis Example 2-2 due to the higher biphenyl component content and the suppression of molecular movement by the biphenyl structure. It is assumed that the price has increased. As a result, the solvent solubility of the hydroxy resin is relatively reduced, so in the subsequent reaction with chloromethylstyrene, many unreacted hydroxyl groups (polar groups with hydrogen bonding properties) remain, and at the same time, flexibility It is inferred that certain vinyl benzyl ether groups were reduced.

(Synthesis example 2-5)
In a 1000ml 4-necked flask, add dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane: 36.2%, 2,4'-dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%) 50 .0 g, 400 g of methyl ethyl ketone, and 80.1 g of chloromethylstyrene were added, the temperature was raised to 60° C., 29.5 g of potassium hydroxide dissolved in 88 g of methanol was added dropwise over 3 hours, and the reaction was further continued for 6 hours. After the reaction was completed, it was filtered, the solvent was distilled off, reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 95.4 g of vinyl resin (vinyl resin E). Vinyl resin E had a vinyl equivalent of 217 g/eq, a hydroxyl equivalent of 17,000 g/eq, a total chlorine content of 400 ppm, an Mn of 440, and a melting point of 80°C.
The reason why the melting point of vinyl resin E is relatively low is inferred as follows. That is, unlike Synthesis Example 2-4, only dihydroxydiphenylmethane is used as a raw material and reacted with chloromethylstyrene, so compared to Synthesis Example 2-2, this is due to the fact that it does not contain a biphenyl component. It is presumed that this is why the melting point of the obtained hydroxy resin was lowered.

Examples 2-1 to 2-5, Comparative Examples 2-1 to 2-4
Vinyl resins A to E obtained in Synthesis Examples 2-1 to 2-5 were used as vinyl resins, and talc (Additive A, average particle size 10 to 15 μm, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was used as an additive to accelerate curing. Perbutyl P (manufactured by NOF Corporation), which is an organic peroxide, was used as an agent, ADEKA STAB AO-60 (manufactured by ADEKA CORPORATION) was used as an antioxidant, and spherical alumina (manufactured by DENKA, DAW-10, average particle) was used as an inorganic filler A. As the inorganic filler B, spherical silica (FB-8S, manufactured by Denka) was mixed in the proportions shown in Table 1 and dissolved in a solvent to form a uniform composition. This composition was applied to a PET film and dried at 130°C for 5 minutes to obtain a resin composition (resin sheet). The composition taken out from the PET film was sandwiched between mirror plates and cured under reduced pressure at 130° C. for 15 minutes and at 210° C. for 80 minutes while applying a pressure of 2 MPa. Table 2 shows the properties of the obtained cured product.

The cured product made of the vinyl resin composition of the example exhibited excellent physical properties such as higher thermal conductivity, lower dielectric constant, and lower dielectric loss tangent compared to the comparative example.

[Effects of the invention and industrial applicability of the second embodiment]
The vinyl resin composition exemplified in the second embodiment has excellent solvent solubility and is suitable for vinyl resin compositions and cured products thereof used in applications such as lamination, molding, casting, and adhesion. This cured product has excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy, so it can be used as a material for encapsulating electrical and electronic components, and for circuit boards. It is suitable for
The vinyl resin composition and cured product according to the second embodiment of the present invention are useful as electronic materials for high-speed communication equipment as materials that easily dissipate heat from electronic components and wiring and cause little signal loss.

Claims

A resin composition containing at least a crystalline resin and an additive, the additive being a layered clay mineral, and containing 1 to 20 parts by weight of the layered clay mineral based on 100 parts by weight of the resin component,
A resin composition characterized in that the crystalline resin has a melting point of more than 80°C and less than 200°C.
The resin composition according to claim 1, wherein the additive is talc or mica.
3. The resin composition according to claim 2, wherein the additive is talc.
The resin composition according to claim 1, wherein the crystalline resin is an epoxy resin and/or a vinyl resin.
The resin composition according to claim 4, wherein the crystalline resin is an epoxy resin with a melting point of more than 80°C and 180°C or less and/or a vinyl resin with a melting point of 90 to 200°C.
The crystalline resin is an epoxy resin and contains a curing agent, and a diffraction peak is detected in a region where the diffraction angle 2θ is 15° or more and less than 25° when measured by X-ray diffraction (XRD) of the cured product of the resin composition. The resin composition according to any one of claims 1 to 5, characterized in that:
The resin composition according to claim 6, wherein the epoxy resin is represented by the following general formula (1-1) or (1-2).

(In formula (1-1), G represents a glycidyl group, and A is independently a single bond, an oxygen atom, a sulfur atom, -SO 2 -, -CO-, or a divalent carbon number of 1 to 6 represents a hydrocarbon group, and n represents a number from 0 to 20.)

(In formula (1-2), Y is independently a single bond, an oxygen atom, a sulfur atom, -SO 2 -, -CO-, -COO-, -CONH-, -CH 2 - or -C( CH 3 ) 2 -. B independently represents a benzonitrile structure or -(CH 2 ) q -, p represents a number from 0 to 15, and q represents a number from 3 to 10.)
The crystalline resin is a vinyl resin, and the vinyl resin has a vinyl equivalent of 150 to 1000 g/eq, a hydroxyl equivalent of 5000 g/eq or more, and a total chlorine amount of 2000 ppm or less. Any of the resin compositions.
The resin composition according to claim 8, wherein the vinyl resin is represented by one or more of the following general formulas (2-1) to (2-3).

(In formula (2-1), R 1 to R 6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.)

(In formula (2-2), A independently represents a single bond, an oxygen atom, a sulfur atom, -SO 2 -, -CO-, or a divalent hydrocarbon group having 1 to 6 carbon atoms, and are independently a benzene ring, a naphthalene ring or a biphenyl ring, and n represents a number from 0 to 20.)

(In formula (2-3), Y is independently a single bond, an oxygen atom, a sulfur atom, -SO 2 -, -CO-, -COO-, -CONH-, -CH 2 - or -C( CH 3 ) 2 -. B independently represents a benzonitrile structure or -(CH 2 ) q -, p represents a number from 0 to 15, and q represents a number from 3 to 10.)
The resin composition according to any one of claims 1 to 5, containing 20 to 90 wt% of an inorganic filler excluding layered clay minerals.
The resin composition according to any one of claims 1 to 5, which is a resin composition that provides a cured product with high thermal conductivity.
The resin composition according to claim 6, which is a resin composition that provides a cured product for high thermal conductivity with a degree of crystallinity of 10% or more.
A cured product obtained by curing the resin composition according to any one of claims 1 to 5.