CN119604586A

CN119604586A - Resin composition and cured product

Info

Publication number: CN119604586A
Application number: CN202380056676.XA
Authority: CN
Inventors: 大村昌己; 大神浩一郎
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2022-08-05
Filing date: 2023-08-03
Publication date: 2025-03-11
Also published as: TW202419577A; WO2024029602A1

Abstract

本发明提供成型性、可靠性优异且高导热性、低吸水性、低热膨胀性、高耐热性、阻燃性优异的固化成型物。另外，适合于溶剂溶解性优异且被用于层叠、成型、铸塑、粘接等用途的树脂组合物及其固化物，该固化物的耐热性、热分解稳定性、导热性、低介电常数、低介质损耗角正切、阻燃性也优异。一种树脂组合物及其固化物，该树脂组合物的特征在于，是至少包含结晶性树脂和添加剂的树脂组合物，添加剂为层状粘土矿物，相对于树脂成分的100重量份，含有1～20重量份的该层状粘土矿物，上述结晶性树脂的熔点大于80℃且为200℃以下。The present invention provides a cured molded product having excellent moldability and reliability, high thermal conductivity, low water absorption, low thermal expansion, high heat resistance, and excellent flame retardancy. In addition, a resin composition and a cured product thereof that are suitable for excellent solvent solubility and are used for lamination, molding, casting, bonding, etc., and the cured product thereof, the cured product also having excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy. A resin composition and a cured product thereof, the resin composition is characterized in that it is a resin composition comprising at least a crystalline resin and an additive, the additive being a layered clay mineral, containing 1 to 20 parts by weight of the layered clay mineral relative to 100 parts by weight of the resin component, and the melting point of the above-mentioned crystalline resin is greater than 80°C and below 200°C.

Description

Resin composition and cured product

Technical Field

The present invention relates to a resin composition useful as an insulating material for electric and electronic materials such as semiconductor packages, laminated boards, and heat dissipating substrates, which are excellent in reliability, and a cured product using the resin composition.

Background

Conventionally, as a method for packaging electric and electronic components such as diodes, transistors, and integrated circuits, and semiconductor devices, for example, a method of packaging with epoxy resin, silicone resin, or the like, or a hermetic packaging method using glass, metal, ceramic, or the like has been employed, but in recent years, resin packaging by transfer molding, which enables mass production while improving reliability and has a cost advantage, has been dominant.

In a resin composition used for resin encapsulation by transfer molding, an encapsulating material composed of a resin composition containing an epoxy resin and a phenolic resin as main components as a curing agent is generally used.

An epoxy resin composition used for protecting elements such as power elements fills an inorganic filler such as crystalline silica at a high density in order to cope with a large amount of heat released from the elements.

The power element includes a single chip element incorporating IC technology, a modularized element, and the like, and it is desired to further improve heat dissipation, heat resistance, and thermal expansion to the packaging material.

In addition, printed circuit boards, packaging materials, casting materials, and the like used in communication devices are also actively studied for high-speed communication technology to increase signal transmission speed with an increase in communication speed and communication traffic. Electronic materials for such applications are required to have a material capable of reducing dielectric loss, and curable resins capable of being multilayered are further required for printed wiring board applications.

On the other hand, there are known various designs such as a method of assembling a heat conductive member such as a copper coin or a copper inlay (patent document 1) or a method of forming a special shape of a filler to be incorporated (patent document 2) as a technique of appropriately cooling a printed circuit board by a heat sink or the like because of a problem such as a decrease in processing speed of an electronic operation member due to heat accumulation caused by a large amount of heat generated from the electronic operation member processing such data having a large amount of information. However, such a method is not preferable because it causes an increase in weight and an increase in size of the apparatus.

As a method for improving the thermal conductivity of the encapsulating material composition, a method of removing heat from electronic operation parts by examining the types and amounts of various fillers has been employed, and for example, attempts have been made to contain inorganic fillers such as crystalline silica, silicon nitride, aluminum nitride, spherical alumina powder, etc. having a large thermal conductivity (patent documents 3 and 4). However, if the content of the inorganic filler is increased, there is a problem that the viscosity increases and the fluidity decreases during molding, and the moldability is impaired. Therefore, there is a limit to methods for simply increasing the content of the inorganic filler.

In view of the above background, a method of improving the thermal conductivity of a composition by increasing the thermal conductivity of a matrix resin itself has been studied. For example, there are proposed an epoxy resin having a liquid crystal property and a rigid mesogenic group, and an epoxy resin composition using the epoxy resin (patent documents 5 and 6). However, the use of aromatic diamine compounds as curing agents for these epoxy resin compositions has a limit to increase the filling rate of inorganic fillers and has a problem in terms of electrical insulation. In addition, when an aromatic diamine compound is used, although the liquid crystalline property of the cured product can be confirmed, the crystallinity of the cured product is low, and the cured product is insufficient in terms of high thermal conductivity, low thermal expansion property, low hygroscopicity, and the like. Further, in order to exhibit liquid crystallinity, a strong magnetic field needs to be applied to orient molecules, and there is also a great restriction on equipment for wide industrial use. In addition, in a system of blending with an inorganic filler, the thermal conductivity of the inorganic filler is overwhelmingly larger than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is improved, it is realistic that the conventional resin does not contribute much to the improvement of the thermal conductivity as a composite material, and a sufficient effect of improving the thermal conductivity cannot be obtained.

Layered clay minerals such as talc are generally used for improving fluidity and reducing linear expansion coefficient. Although the combination of a layered clay mineral and an inorganic filler having a high thermal conductivity has been proposed, it is not effective for the matrix resin itself because of the high thermal conductivity caused by the contact of the inorganic substances (patent document 7).

Patent document 8 discloses a multifunctional vinyl resin having a biphenyl skeleton and having four or more functions as a multifunctional vinyl resin having both high thermal conductivity and low dielectric loss tangent, but does not describe the solvent solubility of the multifunctional vinyl resin and a polyhydric hydroxyl resin as a raw material thereof, nor mention is made of the effect of impurities such as residual polar groups on thermal conductivity.

Prior art literature

Patent literature

Patent document 1 Japanese patent laid-open No. 2009-170493

Patent document 2 International publication No. WO2013/100172

Patent document 3 Japanese patent laid-open No. 11-147936

Patent document 4 Japanese patent laid-open No. 2002-309067

Patent document 5 Japanese patent laid-open No. 11-323162

Patent document 6 Japanese patent laid-open No. 9-118673

Patent document 7 International publication No. WO2013/100174

Patent document 8 International publication No. WO2021/200414

Disclosure of Invention

Accordingly, an object of the present invention is to provide a resin composition and a cured product thereof, which can solve the above-mentioned problems.

For example, the epoxy resin composition of embodiment 1 described below provides a molded article having excellent moldability and reliability, and excellent high thermal conductivity, low thermal expansion, heat resistance, moisture resistance, and flame retardancy, and further provides a molded article in which crystallinity can be observed by XRD.

Further, for example, regarding the vinyl resin composition of embodiment 2 described below, there is provided a vinyl resin composition which is useful for packaging of electric and electronic parts and circuit board materials, etc., and a cured product thereof, and which provides a cured product excellent in solvent solubility, moldability, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy.

The present inventors have made intensive studies and have found that a resin composition containing a layered clay mineral can solve the above-mentioned problems, and that a cured product thereof exhibits at least the effect of thermal conductivity and, in some cases, the effects of low dielectric constant, low dielectric loss tangent, and the like.

Namely, the gist of the present invention is as follows.

[1] A resin composition comprising at least a crystalline resin and an additive, wherein the additive is a layered clay mineral and comprises 1 to 20 parts by weight of the layered clay mineral per 100 parts by weight of the resin component,

The crystalline resin has a melting point of more than 80 ℃ and not more than 200 ℃.

[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 having a melting point of more than 80 ℃ and 180 ℃ or less and/or a vinyl resin having a melting point of 90 to 200 ℃.

[6] The resin composition according to any one of [1] to [5], wherein the crystalline resin is an epoxy resin, the resin composition contains a curing agent, and a diffraction peak is detected in a region having a diffraction angle 2 [ theta ] of 15 DEG or more and less than 25 DEG in measurement of a cured product of the resin composition by an X-ray diffraction method (XRD).

[7] The resin composition according to [6], wherein the epoxy resin is represented by the following general formula (1-1) or (1-2).

(In the formula (1-1), G represents a glycidyl group, 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 n represents a number of 0 to 20)

(In the formula (1-2), Y independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂-、-CO-、-COO-、-CONH-、-CH₂ -or-C (CH ₃)₂ -. B independently represents a benzonitrile structure or- (CH ₂)_q -, p represents a number of 0 to 15), and q represents a number of 3 to 10)

[8] The resin composition according to any one of [1] to [5], wherein the crystalline resin is a vinyl resin having a vinyl equivalent of 150 to 1000g/eq, a hydroxyl equivalent of 5000g/eq or more and a total chlorine content of 2000ppm or less.

[9] The resin composition according to [8], wherein the vinyl resin is represented by any one or more of the following general formulae (2-1) to (2-3).

(In the formula (2-1), R ¹～R⁶ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms)

(In the 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, X independently represents a benzene ring, a naphthalene ring, or a biphenyl ring, and n represents a number of 0 to 20)

(In the formula (2-3), Y independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂-、-CO-、-COO-、-CONH-、-CH₂ -or-C (CH ₃)₂ -. B independently represents a benzonitrile structure or- (CH ₂)_q -, p represents a number of 0 to 15), and q represents a number of 3 to 10)

[10] The resin composition according to any one of [1] to [5], wherein the resin composition contains 20 to 90wt% of an inorganic filler other than a layered clay mineral.

[11] The resin composition according to any one of [1] to [5], wherein the resin composition is a cured product for providing high heat conductivity.

[12] The resin composition according to [6], wherein the resin composition is a cured product for high heat conduction having a 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 article excellent in moldability and reliability, and excellent in high thermal conductivity, low water absorption, low thermal expansion, high heat resistance, and flame retardancy. Further, the resin composition is suitable for use in applications such as lamination, molding, casting and adhesion, for example, and a cured product thereof, which is excellent in heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent and flame retardancy.

Drawings

FIG. 1 is an XRD pattern of a cured molding of the epoxy resin composition obtained in example 1-1 in embodiment 1.

FIG. 2 is an XRD pattern of a cured molding of the epoxy resin composition obtained in comparative example 1-1 in embodiment 1.

FIG. 3 is a GPC chart of a vinyl resin A obtained in Synthesis example 2-1 in embodiment 2.

FIG. 4 is a GPC chart of a vinyl resin B obtained in Synthesis example 2-2 in embodiment 2.

FIG. 5 is a GPC chart of a vinyl resin C obtained in Synthesis example 2-3 in embodiment 2.

FIG. 6 is an FD-MS spectrum of vinyl resin C obtained in Synthesis example 2-3 in embodiment 2.

Detailed Description

The present invention will be described in detail below. In detail, embodiment 1 and embodiment 2 are described below by way of example.

The resin composition of the present invention is a resin composition comprising at least a crystalline resin and an additive, wherein the additive is a layered clay mineral, and 1 to 20 parts by weight of the layered clay mineral is contained per 100 parts by weight of the resin component, and the crystalline resin has a melting point of more than 80 ℃ and not more than 200 ℃.

The resin in the resin composition of the present invention is a crystalline resin having crystallinity at ordinary temperature. The crystalline resin has the same meaning as that generally used in the art, and has a crystal structure. The crystalline resin is a resin that shows a clear endothermic peak in a differential scanning calorimetric analysis.

The crystalline resin is not limited and may be appropriately selected according to the purpose, and examples thereof include acrylic resins, styrene-acrylic resins, polyester resins, epoxy resins, vinyl resins, and the like. These resins may be used in an amount of 1 or 2 or more. Among these crystalline resins, epoxy resins are preferred from the viewpoints of moldability, reliability, high thermal conductivity, low water absorption, heat resistance, low thermal expansion, heat resistance, moisture resistance, and flame retardancy, if the above various properties which are the objects of the present invention are considered. In addition, vinyl resins are preferred from the viewpoints of excellent solvent solubility, moldability, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and excellent flame retardancy.

The crystalline resin of the present invention has a melting point. The melting point is in a range of more than 80 ℃ and less than 200 ℃. Although depending on the resin used, it is preferably 90 ℃ or higher for the purpose of improving the thermal conductivity or for the purpose of reliability and heat resistance. The melting point herein refers to an endothermic peak temperature accompanying melting of the crystal in the differential scanning calorimeter analysis. Resins having a melting point of more than 200 ℃ tend to have strong crystallinity, low solvent solubility and low melt-kneading properties, and cured products of resins having a melting point of 80 ℃ or less tend to fail to improve thermal conductivity.

The layered clay mineral used as the additive in the resin composition of the present invention is also called plate-like particles, and specifically includes smectite-based minerals such as talc, kaolin, mica, montmorillonite, beidellite, hectorite, saponite, nontronite, stevensite, etc., layered sodium silicate such as vermiculite, bentonite, kenemite (kanemite), kenyaite (kenyaite), kenyaite (makatite), etc., mica-group clay minerals such as Na-type tetrafluoromica, li-type tetrafluoromica, na-type fluorobelt mica, li-type fluorobelt mica, etc., and the like. They can be obtained from natural minerals or can be chemically synthesized. 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 preferable, talc and mica are more preferable, and talc is further preferable.

The resin composition contains 1 to 20 parts by weight of a layered clay mineral per 100 parts by weight of the total amount of resin components. Preferably, the content is 5 to 15 parts by weight. If the amount of the layered clay mineral in the resin composition is too small, it may be difficult to sufficiently exert the above-mentioned thermal conductivity. On the other hand, when the content of the layered clay mineral is more than this range, fluidity and heat resistance may be lowered. In addition, when the inorganic filler having high thermal conductivity such as alumina is contained, if the amount of the layered clay mineral is large, the content of the inorganic filler having high thermal conductivity may be insufficient, and the thermal conductivity of the whole may be lowered. The resin component herein refers to a resin, a cured or modified component thereof, and the like. For example, in embodiment 1 described below, the resin component means an epoxy resin, a curing agent, and a curing accelerator if necessary. In embodiment 2 described below, the resin component means a vinyl resin, and a radical polymerization initiator and a modifier, if necessary. The resin component may be used in a modified form as appropriate according to the purpose.

The resin composition of the present invention is not limited as long as the object of the present invention is achieved and the object of the present invention is not impaired, except that the crystalline resin having the melting point in the above-mentioned prescribed range and the lamellar clay mineral as the additive in the above-mentioned prescribed range are used.

For the purpose of describing the specific embodiments of the present invention, embodiment 1 using an epoxy resin as the crystalline resin and embodiment 2 using a vinyl resin as the crystalline resin are exemplified below. As described above, the epoxy resin and the vinyl resin are preferable embodiments satisfying several of various characteristics as the object of the present invention, and the scope of the present invention is not limited to these embodiments.

< Embodiment 1>

Embodiment 1 of the present invention will be described in detail below.

First, embodiment 1 of the present invention relates to an epoxy resin composition using an epoxy resin as a crystalline resin. In embodiment 1, an epoxy resin composition containing a curing agent together with the above-mentioned additive (layered clay mineral) and epoxy resin is preferable. The curing agent is described below. In the epoxy resin composition of embodiment 1, in measurement (XRD) of a cured product thereof by an X-ray diffraction method, a diffraction peak is observed in a predetermined region, and more specifically, a diffraction peak is preferably observed in a region having a diffraction angle 2θ of 15 ° or more and less than 25 °. In general, when XRD measurement is performed on an epoxy resin cured product composed only of an organic substance, the spectrum is broad and no clear peak is detected. When crystallinity is exhibited, a sharp peak can be detected, and the detection range is a region in which 2θ is 15 ° or more and less than 25 °. In addition, when an inorganic substance is contained in the epoxy resin composition, although the peak of the inorganic substance is detected, the peak position is different depending on the crystal structure, and can be distinguished from the peak of the organic substance. When the additive (lamellar clay mineral) is talc, diffraction peaks are observed in the region where 2θ is 28 ° to 29 °. Here, a broad peak is also referred to as an amorphous peak, and a peak having a peak width of 8 ° or more, a sharp peak is also referred to as a crystalline peak, and a peak having a peak width of 5 ° or less, preferably 3 ° or less. That is, the "diffraction peak detected" in embodiment 1 means that the sharp peak (crystalline peak) is preferably detected in a range of 15 ° or more and less than 25 ° in 2θ. The width of the peak is a width between the rising start point and the falling end point of the peak, which is generally parallel to the base line, and which can be obtained by a normal peak analysis method by those skilled in the art.

The epoxy resin component of the epoxy resin composition according to embodiment 1 of the present invention has a melting point of more than 80 ℃ and 200 ℃ or less as described above. The lower limit is preferably 83 ℃ or higher, and more preferably 90 ℃ or higher. On the other hand, the upper limit value is preferably 180 ℃ or less, and more preferably 150 ℃ or less.

The epoxy resin component of the epoxy resin composition according to embodiment 1 of the present invention may be an epoxy resin having 2 or more epoxy groups in the molecule. Examples of the compounds include bisphenol A, bisphenol F, 4 '-dihydroxydiphenyl ether, hydroquinone, 4' -dihydroxybiphenyl, 3', dihydric phenols such as5, 5' -tetramethyl-4, 4 '-dihydroxydiphenyl methane, 4' -dihydroxydiphenyl sulfone, 4 '-dihydroxydiphenyl sulfide, fluorene bisphenol, 2' -biphenol, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, allylated bisphenol A, allylated bisphenol F, allylated phenol novolac, or phenol compounds derived from a ternary or higher phenol compound such as phenol novolak, bisphenol a novolak, o-cresol novolak, m-cresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, tris (4-hydroxyphenyl) methane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, phloroglucinol (phloroglucinol), pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2, 4-phloroglucinol, 2,3, 4-trihydroxybenzophenone, phenol aralkyl resins, naphthol aralkyl resins, dicyclopentadiene resins, or halogenated bisphenols such as tetrabromobisphenol a. These epoxy resins may be used in an amount of 1 or 2 or more. In addition, 1 or 2 or more kinds of epoxy resins having mesogenic groups may be used.

The epoxy resin is preferably a glycidyl ether derived from 4,4 '-dihydroxydiphenyl ether, hydroquinone or 4,4' -dihydroxybiphenyl, or an epoxy resin having a rigid structure such as a mesogenic skeleton and having high thermal conductivity, and particularly preferably an epoxy resin represented by the general formula (1-1) or (1-2). Preferably, the epoxy resin composition contains 50wt% or more of these high thermal conductive epoxy resins based on the entire epoxy resin composition. More preferably 70wt% or more. If the ratio is less than this range, the effect of improving heat resistance, thermal conductivity, and the like in the case of producing an epoxy resin cured product may be small.

In the general formula (1-1), n is a repetition number (number average) and represents a number of 0 to 20. Preferably a mixture of components having different values of n. 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. From the standpoint of thermal conductivity, a is preferably a single bond.

In the general formula (1-2), p is a repetition number (number average) and represents a number of 0 to 15. Preferably a mixture of components having different p values. In addition, Y independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂-、-CO-、-COO-、-CONH-、-CH₂ -or-C (CH ₃)₂ -. Y is preferably a biphenyl structure of a single bond, -SO ₂ -, -CO-, -COO-, -CONH-, particularly preferably a biphenyl structure of a 4,4' -position, on the other hand, Y is preferably an oxygen atom, a sulfur atom, -CH ₂-、-C(CH₃)₂ -. In terms of moldability and solvent solubility, and in addition, B of the formula (1-2) independently represents a benzonitrile structure or- (CH ₂)_q -, q represents a number of 3 to 10. Preferably, B has a structure of at least two in 1 molecule.

The method for producing the epoxy resin used in the epoxy resin composition according to embodiment 1 of the present invention is not particularly limited, and the epoxy resin composition can be produced by reacting a phenolic compound as a raw material with epichlorohydrin. This reaction can be carried out in the same manner as in the usual epoxidation reaction. As the phenolic compound of the raw material, a phenolic compound matching the obtained epoxy resin as described above can be used. In addition, particularly, 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 hydroxyl resin (raw material phenolic compound) represented by the following formula (1-3) with epichlorohydrin.

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

The polyhydric hydroxyl resin (1-3) can be produced by reacting an aromatic crosslinking agent having a biphenyl structure represented by the formula (1-4) with a difunctional phenol compound represented by the formula (1-5).

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

Here, A of the formula (1-5) is the same as that of the formula (1-1).

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' -dihydroxymethyl biphenyl, 4' -dichloromethyl biphenyl, 4' -dibromomethyl biphenyl, 4' -dimethoxymethyl biphenyl, and 4,4' -bisethoxymethyl biphenyl. From the viewpoint of reactivity, 4 '-dihydroxymethylbiphenyl or 4,4' -dichloromethylbiphenyl is preferable, and from the viewpoint of reducing ionic impurities, 4 '-dihydroxymethylbiphenyl or 4,4' -dimethoxymethylbiphenyl is preferable.

In addition, as the difunctional phenol compound of the formula (1-5), specifically, preferably 2,2' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4' -dihydroxybenzophenone, 4' -dihydroxydiphenyl sulfone, 4' -dihydroxydiphenyl sulfide, dihydroxydiphenyl methanes, 2-bis (4-hydroxyphenyl) propane, in particular, 2' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, and dihydroxydiphenylmethane are preferable from the viewpoint of solvent solubility. The dihydroxydiphenyl methane may be a mixture of ortho-, meta-, and para-and the isomer ratio is preferably 40% or less of 4,4' -dihydroxydiphenyl methane. If the amount of 4,4' -dihydroxydiphenyl methane is large, the crystallinity may be high and the solvent solubility may be lowered.

The molar ratio of the aromatic crosslinking agent of the formula (1-4) to the phenol compound of the formula (1-5) is generally in the range of 0.2 to 0.7 mole, more preferably in the range of 0.4 to 0.7 mole, relative to 1 mole of the phenol compound. The reaction may be carried out in the absence of a catalyst or in the presence of an acid catalyst such as an inorganic acid or an organic acid. When 4,4' -dichloromethyl biphenyl is used, the reaction may be carried out in the absence of a catalyst, but in general, the reaction may be carried out in the presence of an acidic catalyst in order to suppress side reactions such as the formation of ether bonds by the reaction of chloromethyl groups with hydroxyl groups. The acidic catalyst may be appropriately selected from known inorganic acids and organic acids, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, lewis acids such as zinc chloride, aluminum chloride, ferric chloride and boron trifluoride, and solid acids.

Typically, the reaction is carried out at 100 to 250 ℃ for 1 to 20 hours. Preferably at 100 to 180 ℃, more preferably 140 to 180 ℃. If the reaction temperature is low, the reactivity is insufficient, time is consumed, and if the reaction temperature is high, the resin may be decomposed.

In the reaction, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc., may be used as the solvent, and of these, ethyl cellosolve, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc. are particularly preferable. After the completion of the reaction, the obtained polyhydroxyl resin may be used as a raw material for the epoxidation reaction in a state where the solvent remains, although the solvent may be removed by a method such as distillation under reduced pressure, water washing or reprecipitation in a poor solvent.

The thus obtained polyhydroxyresins of the formulae (1-3) can be used as a raw material for epoxy resins, and also as an epoxy resin curing agent. Further, the resin composition may be used as a phenolic resin molding material by further combining with a curing agent such as hexamine.

The method for producing the epoxy resin represented by the formula (1-2) is not particularly limited, and the epoxy resin can be produced by reacting a raw material phenolic compound represented by the following formula (1-6) with epichlorohydrin. This reaction can be carried out in the same manner as in the usual epoxidation reaction. In the case where the starting material is a mixture with a compound of p=0 or 1 represented by the general formula (1-6), the epoxy resin obtained by the present method includes not only the epoxy resin of embodiment 1 of the present invention but also a mixture of the epoxy resin of embodiment 1 of the present invention and an epoxide of a compound of p=0 or 1 represented by the general formula (1-2) as described above.

Here, Y, B and p of the formula (1-6) are the same as those of the above formula (1-2).

The hydroxyl equivalent (g/eq) of the phenolic compound represented by the formula (1-6) (in the case of a mixture with a compound having p=0 or 1) is preferably 150 to 230, more preferably 170 to 220. In addition, the melting point is preferably 140 ℃ to 300 ℃, more preferably 150 ℃ to 250 ℃.

Here, the raw material phenolic compound represented by the formula (1-6) is not limited in production as long as it has a predetermined structure, and is suitably obtained by reacting one or both of a benzonitrile compound and a dihaloalkyl compound with a dihydroxy compound having a Y group in the formula (1-6) in the presence of a basic catalyst.

Examples of the benzonitrile compound include 2, 4-dichlorobenzonitrile, 2, 5-dichlorobenzonitrile, 2, 6-dichlorobenzonitrile, 3, 5-dichlorobenzonitrile, 2, 4-dibromobenzonitrile, 2, 5-dibromobenzonitrile, 2, 6-dibromobenzonitrile, 3, 5-dibromobenzonitrile, etc., examples of the dihaloalkyl compound include 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, etc., and examples of the dihydroxy compound having a Y group in the formula (1-6) include 4,4' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl sulfone, 4' -dihydroxybenzophenone, bisphenol A, bisphenol F, etc.

The method for producing the raw material phenolic compound is not particularly limited, and more specific conditions include, for example, the method described in WO 2021/201046.

The reaction of the above-mentioned raw material phenolic compound with epichlorohydrin may be carried out, for example, by dissolving the phenolic compound in an excessive amount of epichlorohydrin and then reacting for 1 to 10 hours at 50 to 150 ℃, preferably 60 to 100 ℃ in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The amount of the alkali metal hydroxide used in this case is in the range of 0.8 to 2.0 mol, preferably 0.9 to 1.5 mol, based on 1 mol of the hydroxyl groups in the phenolic compound. An excess of epichlorohydrin may be used relative to the hydroxyl groups in the phenolic compound, and is usually 1.5 to 15 moles relative to 1 mole of hydroxyl groups in the phenolic compound. After the completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, and the solvent is distilled off after filtration and washing with water to remove an inorganic salt, thereby obtaining the target epoxy resin.

The purity of the epoxy resin, in particular, the smaller the amount of hydrolyzable chlorine, is, the better from the viewpoint of improving the reliability of the electronic component to be used. Although not particularly limited, it is preferably 1000ppm or less, more preferably 500ppm or less. In embodiment 1 of the present invention, the hydrolyzable chlorine is a value measured by the following method. That is, 0.5g of the sample was dissolved in twoAfter 30ml of alkane, 10ml of 1N-KOH was added, and after 30 minutes of boiling reflux, the mixture was cooled to room temperature, 100ml of 80% acetone water was further added, and the resulting mixture was subjected to potentiometric titration with 0.002N-AgNO ₃ aqueous solution.

As the curing agent used in the epoxy resin composition according to embodiment 1 of the present invention, it is generally known that dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines and the like can be used as the curing agent for epoxy resins. Among these, in the field where high electrical insulation is required for a semiconductor packaging material or the like, polyhydric phenols are preferably used as a curing agent. Specific examples of the curing agent are shown below.

Examples of the polyhydric phenols include dihydric phenols such as bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, 4 '-biphenol, 2' -biphenol, hydroquinone, resorcinol, and naphthalene diphenol, and three or more phenols such as tris (4-hydroxyphenyl) methane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, and polyvinyl phenol. Further, there are polyhydric phenol compounds synthesized from dihydric phenols such as phenols, naphthols, bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, 4 '-biphenol, 2' -biphenol, hydroquinone, resorcinol, and naphthalene diphenol, and condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, parahydroxybenzaldehyde, and paraxylylene glycol.

Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenyl succinic anhydride, nadic anhydride, and trimellitic anhydride.

Examples of the amine-based curing agent include aromatic amines such as 4,4' -diaminodiphenyl methane, 4' -diaminodiphenyl propane, 4' -diaminodiphenyl sulfone, m-phenylenediamine, and p-xylylenediamine, and aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

In the epoxy resin composition, 1 or 2 or more of these curing agents may be used in combination.

The mixing ratio of the epoxy resin and the curing agent is preferably in the range of 0.8 to 1.5 in terms of equivalent ratio of the epoxy group to the functional group in the curing agent. When the amount is outside this range, unreacted epoxy groups or functional groups in the curing agent may remain after curing, and reliability regarding the encapsulating function may be lowered.

An oligomer or a polymer compound such as a polyester, a polyamide, a polyimide, a polyether, a polyurethane, a petroleum resin, an indene coumarin resin, or a phenoxy resin may be appropriately blended as another modifier to the epoxy resin composition of embodiment 1 of the present invention. The amount of the additive 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 embodiment 1 of the present invention may contain additives such as inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, and fluidity improvers other than the above-mentioned layered clay minerals such as mica and talc. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, calcium carbonate, alumina, and hydrated alumina, and the blending amount in the case of using the inorganic filler for a semiconductor encapsulating material is preferably 70 wt% or more, and more preferably 80 wt% or more. The preferable amount of the resin to be blended when used for a heat dissipating substrate is 20 to 90 wt%, more preferably 40 to 60 wt%, because fluidity is required.

Examples of pigments include organic or inorganic extender pigments and flake pigments. Examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organobentonite-based.

In the epoxy resin composition of embodiment 1 of the present invention, a curing accelerator may be used as needed. Examples thereof include amines, imidazoles, organic phosphines, lewis acids, and the like, specifically, 1, 8-diazabicyclo (5, 4, 0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tertiary amines such as tris (dimethylaminomethyl) phenol, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, and the like, and organic phosphines such as tetraphenylphosphineTetraphenyl borate, tetraphenyl groupEthyl triphenylborate, tetrabutylTetra-substitution of tetrabutyl borate or the likeTetraphenylboron salts such as tetra-substituted borates, 2-ethyl-4-methylimidazole tetraphenylborates and N-methylmorpholine tetraphenylborates. The amount of the additive is usually in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total resin components.

Further, as necessary, a releasing agent such as carnauba wax or OP wax, a coupling agent such as γ -glycidoxypropyl trimethoxysilane, a coloring agent such as carbon black, a flame retardant such as antimony trioxide, a stress reducing agent such as silicone oil, a lubricant such as calcium stearate, and the like may be used in the epoxy resin composition of embodiment 1 of the present invention.

The epoxy resin composition according to embodiment 1 of the present invention can be prepared into a prepreg by impregnating fibrous materials such as glass cloth, aramid nonwoven fabric, and polyester nonwoven fabric such as liquid crystal polymer with a varnish in which an organic solvent is dissolved, and then removing the solvent. Further, a laminate may be formed by coating a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film, as the case may be.

When the epoxy resin composition according to embodiment 1 of the present invention is heat-cured, the resin cured product according to embodiment 1 of the present invention can be produced. The cured product can be obtained by molding an epoxy resin composition by a method such as casting, compression molding, transfer molding, or the like. The temperature at this time is usually in the range of 120 to 220 ℃. Further, the molded product having a crystallinity of 10% or more has high thermal conductivity, and is suitable for high thermal conductivity applications such as a heat dissipating substrate. In addition, the crystallinity is affected by temperature control during molding, and if molding is performed at a high temperature exceeding 200 ℃, the crystallinity becomes amorphous, and it is difficult to obtain a molded article in which crystallinity is observed, and it is preferable to heat the molded article stepwise. More preferably, the molding is performed by heating at a temperature of 120 to 200 ℃ in a stepwise manner in a range of 30 seconds to 1 hour (preferably 1 minute to 30 minutes). After molding, the above-mentioned crystallinity can be adjusted by post-curing. The post-curing temperature is 130 ℃ to 250 ℃ and the time is 1 hour to 24 hours, and the post-curing is preferably performed at a temperature 5 ℃ to 40 ℃ lower than the endothermic peak temperature obtained by the differential scanning calorimetric analysis apparatus and the condition measurement shown in the examples, for 1 hour to 24 hours. The crystallinity of the molded product (cured product) can be determined by the method described in the examples based on the ratio of the crystalline peaks.

< Embodiment 2 >

Embodiment 2 of the present invention will be described in detail below.

Embodiment 2 of the present invention relates to a vinyl resin composition using a vinyl resin as a crystalline resin. In embodiment 2, the vinyl resin used in the vinyl resin composition is a resin having crystallinity at ordinary temperature, and the melting point thereof is more than 80 ℃ and 200 ℃ or less as described above. The melting point is preferably in the range of 90 to 200 ℃, more preferably 110 to 180 ℃. As described above, the melting point refers to the endothermic peak temperature accompanying the melting of the crystal in the differential scanning calorimeter analysis. Vinyl resins having a melting point of more than 200 ℃ tend to have strong crystallinity, low solvent solubility and low melt-kneading properties, and cured products of vinyl resins having a melting point of less than 90 ℃ tend to fail to improve thermal conductivity.

The vinyl equivalent of the vinyl resin used in embodiment 2 of the present invention is preferably in the range of 150 to 1000 g/eq. More preferably 200 to 500 g/eq. If the amount is larger than this range, the reactivity tends to be low, and unreacted components are generated during curing, so that the heat resistance and reliability tend to be low. If the content is less than this range, the solvent solubility and melt-kneading property tend to be low, and the cured product tends to become hard and brittle, and the film properties tend to be low.

Regarding the polar groups of the vinyl resin used in embodiment 2 of the present invention, the hydroxyl equivalent weight is preferably 5000g/eq or more, and the total chlorine amount is preferably 2000ppm or less.

The vinyl resin used in embodiment 2 of the present invention can be obtained by reacting the hydroxyl groups of a hydroxyl resin with an aromatic vinylating agent represented by chloromethylstyrene, but in this case, the hydroxyl groups of the hydroxyl resin remaining unreacted are too many, and when the hydroxyl equivalent is less than 5000g/eq, curing becomes insufficient, and thermal conductivity and heat resistance tend to decrease. Further, since the hydroxyl group is a polar group, it tends to remain as a barrier to decrease in dielectric constant and dielectric loss tangent. The hydroxyl equivalent is more preferably 8000g/eq or more, still more preferably 10000g/eq or more.

On the other hand, as the chlorine component, there are a chlorine component derived from chloromethylstyrene and a chlorine component derived from a crosslinking agent in a raw material for producing a hydroxyl resin. When the solvent solubility of the vinyl resin is low, it is difficult to remove these chlorine components. When more than 2000ppm of chlorine component remains, the decrease in dielectric constant and dielectric loss tangent is inhibited, and the curing reaction is inhibited, so that the thermal conductivity and heat resistance tend to be lowered. The total chlorine content is more preferably 1000ppm or less, and still more preferably 800ppm or less.

The vinyl resin used in embodiment 2 of the present invention can be suitably obtained by reacting a hydroxyl resin (hydroxyl compound) with an aromatic vinylating agent. Although not limited thereto, for example, vinyl resins having structures represented by the following formulas (2-1) to (2-3) are preferable. The structures of the following formulae (2-1) to (2-3) are structural skeletons which can suppress intramolecular and intermolecular molecular mobility and can expect thermal conductivity, and are excellent in solvent solubility and melt-kneading property, so that a uniform cured product can be molded and thermal conductivity can be exhibited, and thus a resin which achieves the object of the present invention is a preferred embodiment.

< Vinyl resin of formula (2-1) >)

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

R ¹～R⁶ in the formula (2-4) is the same as in the formula (2-1).

In the formula (2-1) and the formula (2-4), R ¹～R⁶ is 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. Alkyl groups having more than 6 carbon atoms are difficult to inhibit molecular movement, and there is also concern that compatibility is lowered. In addition, the bulky structure with large steric hindrance may have a problem that the solvent solubility is lowered due to an increase in crystallinity. More preferred structures are methyl or phenyl. In formula (2-1) and formula (2-4), R ¹～R⁶ may be a mixture of different structures.

The substitution position of the vinyl benzyl ether of the vinyl resin of formula (2-1) is not particularly limited, but is preferably para-position with respect to the methine group to which 3 aromatic rings are bonded from the viewpoints of thermal conductivity and heat resistance. In particular, it is more preferable that all of 3 vinyl benzyl ethers are para-position.

The number average molecular weight (Mn) of the vinyl resin of the formula (2-1) is preferably 2000 or less, more preferably 1500 or less. Further, the polymer may contain a multibranched compound represented by the following general formula (2-5). T in the formula (2-5) is a repetition number (number average) and represents a number of 0 to 20. Preferably a mixture of components having different values of t. From the standpoint of thermal conductivity, the content of t=0 body is preferably 50 weight percent (wt%) or more, more preferably 80wt% or more.

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

Examples of the monohydric phenol compound include monoalkylphenols such as phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-octylphenol, p-t-butylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, dialkylphenols such as 2, 5-xylenol, 3, 4-xylenol, 2, 4-xylenol and 2, 6-xylenol, trialkylphenols such as 2,3, 5-trimethylphenol and 2,3, 6-trimethylphenol, and hydroxybiphenyl such as 2-phenylphenol, 4-phenylphenol, 3-benzyl-1, 1 '-biphenyl-2-ol, 3-benzyl-1, 1' -biphenyl-4-ol, 3-phenylphenol and 2, 6-diphenylphenol. 2, 5-xylenol, 2, 6-xylenol, and 2-phenylphenol are particularly preferred from the viewpoints of solvent solubility, reactivity, and feedability. Only 1 kind of these phenol compounds may be used, or 2 or more kinds may be used in combination.

Examples of the aromatic aldehyde include hydroxybenzaldehydes such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-3, 5-dimethylbenzaldehyde, 4-hydroxy-2, 5-dimethylbenzaldehyde, and 3, 5-diethyl-4-hydroxybenzaldehyde. From the viewpoints of heat resistance and thermal conductivity, 4-hydroxybenzaldehyde is preferable.

The polycondensation of the phenol compound with the aromatic aldehyde may use an acid catalyst, and examples thereof include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, and the like. The acid catalyst may be used in an amount of 1 or 2 or more. Among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferable because of their excellent activity. The acid catalyst may be added before the reaction or may be added during the reaction.

Polycondensation of phenol compound with aromatic aldehyde the polycondensate can be obtained in the presence of a solvent as required. Examples of the solvent include monohydric alcohols such as methanol, ethanol and propanol, polyhydric alcohols such as ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, propylene glycol, diethylene glycol, polyethylene glycol and glycerin, dihydric alcohol ethers such as 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol methylethyl ether and ethylene glycol monophenyl ether, and 1, 3-diAlkane, 1, 4-diCyclic ethers such as alkanes and tetrahydrofuran, glycol esters such as ethylene glycol acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. The solvent may be used in an amount of 1 or 2 or more. Among these solvents, 2-ethoxyethanol is preferred because of its excellent solubility in the resulting compound.

The reaction temperature at the time of polycondensation of the phenol compound and the aromatic aldehyde is preferably in the range of 20 to 140 ℃, more preferably in the range of 80 to 110 ℃.

The ratio of the phenol compound to the aromatic aldehyde to be added is preferably in the range of 1/0.1 to 1/0.5, more preferably in the range of 1/0.3 to 1/0.5 in terms of a molar ratio, from the viewpoint that the phenol compound after the reaction can be easily removed by reprecipitation or the like.

The vinyl resin of the formula (2-1) can be suitably obtained by reacting a trifunctional hydroxy compound with an aromatic vinylating agent. Although not limited thereto, for example, a suitable vinyl resin in 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. This reaction can be carried out in the same manner as in the known vinylation reaction.

The blending ratio is preferably 0.8 to 1.2 equivalents of the aromatic vinyl agent (for example, chloromethylstyrene) to 1.0 equivalent of the hydroxyl group as the functional group of the trifunctional hydroxyl compound. However, when 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 is preferable, and chloromethylstyrene is particularly preferable. In addition, bromomethylstyrene and isomers thereof, and substituted materials and the like can be mentioned. For the substitution site of the halomethyl matrix, for example, in the case of halomethyl styrene, the 4-position is preferable, and the 4-position is preferably 60% by weight or more of the whole.

The reaction of the trifunctional hydroxy compound with the aromatic vinylating agent may be carried out in the absence of a solvent or in the presence of a solvent. The hydroxyl compound may be reacted by adding an aromatic vinyl agent and a metal hydroxide, and the resulting metal salt may be removed by filtration, washing with water, or the like. 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 the metal hydroxide include sodium hydroxide and potassium hydroxide, but are not limited thereto.

The reaction for vinylation is preferably at a temperature of 90 ℃ or less, more preferably at a temperature of 70 ℃ or less. Above this temperature, the vinyl benzyl ether gene may undergo self-polymerization by heat, and the reaction may be difficult to control. In order to inhibit self-polymerization, polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitrosos, nitrone compounds, oxygen and the like can be used.

The end point of the reaction can be determined by tracking the residual amount of halomethylstyrene as an aromatic vinyl agent by various chromatographs such as GPC, and the reaction rate can be adjusted by the type, amount, addition rate, solid content concentration, and the like of the metal hydroxide.

< Vinyl resin of formula (2-2), vinyl resin of formula (2-3) >)

As the vinyl resin used in embodiment 2 of the present invention, in addition to the vinyl resin represented by the formula (2-1), the vinyl resins represented by the formulas (2-2) and (2-3) are also preferable. These vinyl resins may be used in combination, and preferably contain 50% by weight or more of the total resin components, of the vinyl resins represented by the formulae (2-1) to (2-3). More preferably, the content is 70wt% or more. If the ratio is smaller than this ratio, the effect of improving heat resistance, thermal conductivity, and the like in the case of producing a cured product may be small.

[ Vinyl resin of (2-2) ]

In the above formula (2-2), n is a repetition number (number average) and represents a number of 0 to 20. In general, 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, for a mixture of components having different values of repetition number (n).

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, a naphthalene ring, or a biphenyl ring. From the standpoint of thermal conductivity, it is preferable that A be a single bond and X be a biphenyl ring. The substitution position of 2 vinyl benzyl ether groups bonded to the biphenyl structure having a preferably contains at least a2, 2' body. In the formula (2-2), A is a single bond, that is, when both ends are biphenyl rings, the substitution positions of the 2 vinyl benzyl ether groups bonded to the A are preferably 4,4' position and 2,2' position, and the ratio of the biphenyl groups at both ends is preferably 40 to 90 mol% of the whole 2,2' position. In the case where A is other than a single bond, that is, both ends of the vinyl resin are other than biphenyl rings, for example, a diphenylmethane structure, the substitution positions of the 2 vinyl benzyl ether groups bonded thereto are preferably 30 to 100 mol%.

The vinyl resin of the formula (2-2) is preferably a multifunctional vinyl resin represented by the following formula (2-6).

E and f in the formula (2-6) are repeated numbers (number average) and represent numbers of 0 to 20. Preferably 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 the amount is less than 0.50, the effects of heat resistance and high thermal conductivity tend to be small, and when the amount is more than 0.95, the crystallinity tends to be high, and the solvent solubility tends to be low. 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.

A is the same as the above formula (2-2).

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

The ratio A, e, f, e/(e+f) in the polyhydric hydroxyl resin of the formula (2-7) is the same as that of the polyfunctional vinyl resin of the formula (2-6). The hydroxyl equivalent of the polyhydric hydroxyl resin represented by the formula (2-6) is preferably 100 to 350g/eq. The polyfunctional vinyl resin represented by the formula (2-6) can be obtained by partially or wholly vinylating these hydroxyl groups.

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

Wherein Z in the 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 4,4' -dihydroxybiphenyl represented by the formula (2-8) to the difunctional phenol compound represented by the formula (2-10) as the synthetic raw material at the time of charging is preferably 0.50 to 0.95, more preferably 0.70 to 0.95. When the ratio of 4,4' -dihydroxybiphenyl is smaller than this range, heat resistance and high thermal conductivity tend to be insufficient, and when the ratio is larger than this range, the crystallinity tends to be strong, and the solvent solubility tends to be lowered.

The difunctional phenol compounds of the formula (2-10) are specifically 2,2' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4' -dihydroxybenzophenone, 4' -dihydroxydiphenyl sulfone, 4' -dihydroxydiphenyl sulfide, dihydroxydiphenyl methane and 2, 2-bis (4-hydroxyphenyl) propane, and 2,2' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether and dihydroxydiphenyl methane are preferable from the viewpoint of solvent solubility. The dihydroxydiphenyl methane may be a mixture of ortho-, meta-, and para-and the isomer ratio is preferably 40% or less of 4,4' -dihydroxydiphenyl methane. If the amount of 4,4' -dihydroxydiphenyl methane is large, the crystallinity may be high and the solvent solubility may be lowered.

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' -dihydroxymethyl biphenyl, 4' -dichloromethyl biphenyl, 4' -dibromomethyl biphenyl, 4' -dimethoxymethyl biphenyl, and 4,4' -bisethoxymethyl biphenyl. From the viewpoint of reactivity, 4 '-dihydroxymethylbiphenyl or 4,4' -dichloromethylbiphenyl is preferable, and from the viewpoint of reducing ionic impurities, 4 '-dihydroxymethylbiphenyl or 4,4' -dimethoxymethylbiphenyl is preferable.

The molar ratio of the phenol to the aromatic crosslinking agent in the reaction of the phenol represented by the formula (2-11) is generally in the range of 0.2 to 0.7 mole, more preferably in the range of 0.4 to 0.7 mole, relative to 1 mole of the phenol. If the amount is less than 0.2 mol, the obtained polyhydroxyl resin represented by the formula (2-2) has a high n=0-isomer ratio, and in particular, if the amount of 4,4' -dihydroxybiphenyl represented by the formula (2-8) is too large, there is a concern that the solubility such as crystallinity may be lowered. On the other hand, if the amount is more than 0.7 mol, the high molecular weight component becomes large, and it may be difficult to stably produce the polymer.

The reaction of phenols with the aromatic crosslinking agent may be carried out in the absence of a catalyst or in the presence of an acid catalyst such as an inorganic acid or an organic acid. When 4,4' -dichloromethyl biphenyl is used, the reaction may be carried out in the absence of a catalyst, but in general, the reaction may be carried out in the presence of an acidic catalyst in order to suppress side reactions such as ether bond formation caused by the reaction of chloromethyl groups with hydroxyl groups. The acidic catalyst may be appropriately selected from known inorganic acids and organic acids, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid and trifluoromethanesulfonic acid, lewis acids such as zinc chloride, aluminum chloride, ferric chloride and boron trifluoride, and solid acids.

In the reaction, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc., may be used as the solvent, and of these, ethyl cellosolve, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc. are particularly preferable. After the completion of the reaction, the obtained polyhydroxyl resin may be used as a starting material for the vinylation reaction in a state where the solvent remains, although the solvent may be removed by a method such as distillation under reduced pressure, water washing or reprecipitation in a poor solvent.

The vinyl resin of the formula (2-2), preferably the multifunctional vinyl resin represented by the formula (2-6), can be suitably obtained by reacting a polyhydric hydroxyl resin with an aromatic vinylating agent. For example, the polyfunctional vinyl resin represented by the above formula (2-6) can be obtained by reacting the polyhydric hydroxyl resin represented by the above formula (2-7) with chloromethyl styrene. This reaction can be carried out in the same manner as in the known vinylation reaction.

The mixing ratio, the type of the aromatic vinyl agent, the reaction conditions, the confirmation of the reaction end point, and other aspects may be the same as those in the case of obtaining the vinyl resin of the above formula (2-1).

[ Vinyl resin of (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-、-CH₂ -, or-C (CH ₃)₂ -. B independently represents a benzonitrile structure or- (CH ₂)_q -, preferably comprising a benzonitrile structure in at least 1 molecule), more preferably having a benzonitrile structure and- (CH ₂)_q -both in at least 1 molecule, q represents a number of 3 to 10, Y is preferably a direct bond biphenyl structure, -SO ₂ -, -CO-, -COO-, or-CONH-, more preferably a direct bond biphenyl structure, wherein in particular, the biphenyl structure at the 4,4' -position is preferred, on the other hand, an oxygen atom, a sulfur atom, -CH ₂-、-C(CH₃)₂ -. Is preferred as shown in terms of moldability and solvent solubility, the vinyl resin of the formula (2-3) may be a mixture of different structures of each Y, and the number of 0 to 15 is preferably an average value of 0.5.5 to 1, and the number of p is preferably a mixture of different values of p.1 to 3, preferably a number of 0.5.

The vinyl resin of the formula (2-3) may be a mixture with a compound of p=0, and the compound of p=0 is preferably 40% or less in terms of area% (GPC area%) measured by gel permeation chromatography. More preferably 35% or less. When the compound having p=0 is contained in an amount of more than 40%, the crystallinity tends to be strong, the melting point exceeds 200 ℃, and the solvent solubility tends to be low. In addition, the compound having p of more than 15 has low reactivity, and if unreacted components are generated at the time of curing, heat resistance tends to be lowered.

The vinyl resin of the formula (2-3) may be a mixture of different structures, as shown in "independent" in B, and may have a high thermal conductivity, moldability and solvent solubility adjusted, and the ratio of the benzonitrile structure to the alkyl structure is preferably 50 mol% or more, more preferably 70 mol% or more, based on the mass of the raw material compound, and the alkyl structure is preferably less than 50 mol%, more preferably 10 mol% to 40 mol%, and the alkyl structure is more than 50 mol%.

The alkyl structure represented by- (CH ₂)_q) -wherein q is a repetition number and is a number of 3 to 10, more preferably a number of 4 to 8, and if it is less than 3, the flexibility tends to be low and the effect of relaxing the crystallinity tends to be low, and if it is more than 10, the thermal conductivity and heat resistance of the cured product tend to be significantly lowered.

Specifically, vinyl resins represented by the following formulas (2 to 12) can be preferably exemplified.

(Wherein g and h each independently represent a number of 1 to 15, and q represents a number of 3 to 10)

The vinyl resin of the formula (2-3) can be suitably obtained by reacting a hydroxyl 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 formula (2-13) with chloromethylstyrene. This reaction can be carried out in the same manner as in the known vinylation reaction.

(Wherein Y independently represents a direct bond, an oxygen atom, a sulfur atom, -SO ₂-、-CO-、-COO-、-CONH-、-CH₂ -, or-C (CH ₃)₂ -. B independently represents a benzonitrile structure or- (CH ₂)_q -, preferably at least 1 contains a benzonitrile structure.) more preferably, at least 1 contains both a benzonitrile structure and an alkyl structure represented by- (CH ₂)_q -, p and q are each independently p represents 0 to 15, q represents a number of 3 to 10)

The hydroxyl equivalent (g/eq) of the hydroxyl resin represented by the formula (2-13) (in the case of a mixture with a compound having p=0) is preferably 150 to 300, more preferably 200 to 270. The number average molecular weight (Mn) is preferably 350 to 800, more preferably 450 to 600.

P is synonymous with p in the vinyl resin of formula (2-3), and represents the number of repetition, 0 to 15. Preferably, the number may be 1 to 15. Preferably a mixture of components having different p values. The p value (average value) is preferably 1.0 to 3.0, more preferably 1.5 to 2.5.

The hydroxyl resin (phenolic compound) represented by the formula (2-13) is not limited in production as long as it has a predetermined structure, and can be suitably obtained by reacting one or both of a benzonitrile compound and a dihaloalkyl compound with a dihydroxy compound having a Y group 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, 2, 4-dibromobenzonitrile, 2, 5-dibromobenzonitrile, 2, 6-dibromobenzonitrile, 3, 5-dibromobenzonitrile, etc., examples of the dihaloalkyl compound include 1, 3-dibromopropane, 1, 4-dibromobutane, 1, 5-dibromopentane, 1, 6-dibromohexane, etc., and examples of the dihydroxyl compound having a Y group include 4,4' -dihydroxybiphenyl, 4' -dihydroxydiphenyl ether, 4' -dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl sulfone, 4' -dihydroxybenzophenone, bisphenol a, bisphenol F, etc.

For more specific conditions for the production of the hydroxy resin (phenolic compound), reference is made to, for example, WO 2021/201046.

The vinyl resin used in embodiment 2 of the present invention can be cured alone, but is preferably used as a vinyl resin composition containing various other additives in addition to the above-mentioned layered clay minerals such as talc and mica. As one of the other additives, in particular, a radical polymerization initiator such as an azo compound or an organic peroxide may be blended to cure the mixture for the purpose of accelerating the curing. The radical polymerization initiator may be blended in a range of, for example, 0.01 to 10 parts by weight relative to 100 parts by weight of the vinyl resin.

The vinyl resin composition of embodiment 2 of the present invention contains a vinyl resin and a lamellar clay mineral as an additive as essential components, but other vinyl compounds and other thermosetting resins may be blended, and examples thereof include epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoatesAn oxazine resin, and the like.

For improving the thermal conductivity, for example, inorganic fillers other than the above layered clay minerals, such as glass cloth, carbon fiber, alumina, and boron nitride, may be blended.

In order to impart higher thermal conductivity, the inorganic filler is preferably high in thermal conductivity. The thermal conductivity is preferably 20W/mK or more, more preferably 30W/mK or more, and still more preferably 50W/mK or more. Further, at least a part of the inorganic filler preferably 50wt% or more has a thermal conductivity of 20W/mK or more. The average thermal conductivity of the inorganic filler as a whole is more preferably 20W/mK or more, 30W/mK or more, and 50W/mK or more.

Examples of the inorganic filler having such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide. The content of the inorganic filler in the vinyl resin composition according to embodiment 2 of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, in the case of using the inorganic filler as a semiconductor encapsulating material. The preferable amount to be blended when used for a heat dissipating substrate is 20 to 90 wt%, more preferably 40 to 60 wt%, because fluidity is required.

Various other additives may be used to improve the adhesion and the handling of the composition, such as a silane coupling agent, an antifoaming agent, an internal mold release agent, and a flow control agent. In addition, various known additives such as a colorant, a flame retardant, a thixotropic agent, and the like may be used within the scope of the object of the present invention.

The vinyl resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone, impregnated in a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heat-dried to obtain a prepreg, and the prepreg is heat-pressed to obtain a cured product or the like.

The vinyl resin composition according to embodiment 2 of the present invention may be applied to a sheet-like material such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film to form a laminate, or a resin sheet obtained by heat drying may be subjected to hot press molding to obtain a cured product.

The vinyl resin composition of embodiment 2 of the present invention is suitable for providing a cured product having high thermal conductivity, that is, for use as a cured product for providing high heat conductivity. When the cured product of the vinyl resin composition according to embodiment 2 of the present invention contains an inorganic filler, the thermal conductivity is preferably 8W/m·k or more, more preferably 10W/m·k or more. When the inorganic filler is not contained, the thermal conductivity is preferably 0.25W/mK or more, more preferably 0.30W/mK or more.

Examples

The present invention will be specifically described below with reference to examples, comparative examples, and the like. The invention is not limited to these. Unless otherwise specified, "parts" means parts by weight and "%" means% by weight.

< Example of embodiment 1>

Embodiment 1 of the present invention will be described in further detail by way of examples.

Synthesis example 1-1 (preparation of epoxy resin A)

100.0G of 4,4' -dihydroxydiphenyl ether was dissolved in 460g of epichlorohydrin and 70g of diethylene glycol dimethyl ether, and 90.8g of a 48% aqueous sodium hydroxide solution was added dropwise under reduced pressure (about 130 Torr) at 60℃for 3 hours. During this time, the water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for 1 hour, after dehydration, epichlorohydrin was distilled off, 580g of toluene was added, and then the salt was removed by washing with water. Thereafter, after water was removed by separation, toluene was distilled off under reduced pressure to obtain 126g of an epoxy resin (epoxy resin a) in the form of white crystals. The epoxy equivalent was 163, the hydrolyzable chlorine was 150ppm, the melting point was 83℃and the viscosity at 150℃was 10 mPas. The epoxy resin obtained from 4,4' -dihydroxydiphenyl ether was found to have n=0 (monomer) of 91.2% by GPC measurement. n=1 or more is 8.8%.

Synthesis examples 1 to 2 (preparation of epoxy resin B)

50.0G of hydroquinone and 100.0g of 4,4' -dihydroxybiphenyl were dissolved in 1000g of epichlorohydrin and 150g of diethylene glycol dimethyl ether, and 16.5g of 48% sodium hydroxide was added at 60℃and stirred for 1 hour. Thereafter, 148.8g of a 48% aqueous sodium hydroxide solution was added dropwise under reduced pressure (about 130 Torr) over 3 hours. During this time, the water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for 1 hour, after dehydration, epichlorohydrin was distilled off, 600g of methyl isobutyl ketone was added, and then the salt was removed by washing with water. Thereafter, 13.5g of 48% sodium hydroxide was added thereto at 85℃and stirred for 1 hour, followed by washing with 200mL of warm water. Thereafter, after water was removed by liquid separation, methyl isobutyl ketone was distilled off under reduced pressure to obtain 224g of an epoxy resin (epoxy resin B) in the form of white crystals. The epoxy equivalent was 139, the hydrolyzable chlorine was 320ppm, the melting point was 125℃and the viscosity at 150℃was 3.4 mPas. The epoxy resin obtained from 4,4' -dihydroxybiphenyl was found to have n=0 (monomer) of 67.2% by GPC measurement. In addition, the method comprises the following steps. The epoxy resin obtained from hydroquinone has n=0 (monomer) of 23.1%. n=1 or more is 9.7%.

Synthesis examples 1 to 3 (preparation of epoxy resin C)

After dissolving 115.7g of 4,4' -dihydroxybiphenyl in 700g of NMP in a 2L four-necked separable flask, 56.7g of potassium carbonate was added thereto, and the mixture was heated to 120℃under nitrogen flow with stirring. Thereafter, 35.6g of 2, 6-dichlorobenzonitrile was added thereto, and the reaction was continued at 145℃for 6 hours. 49.2g of acetic acid was added to the reaction mixture to neutralize the reaction mixture, and NMP was distilled off under reduced pressure. MIBK 500mL was added to the reaction mixture to dissolve the product, and then the salt was removed by washing with water. Thereafter, MIBK was removed by distillation under reduced pressure to obtain 129g of a hydroxy resin. The hydroxyl equivalent weight of the resulting hydroxyl resin was 170g/eq. And the melting point was 272 ℃. 50.0g of the obtained hydroxy resin, 380g of epichlorohydrin and 96g of diethylene glycol dimethyl ether (diglyme) were charged, and 27.5g of a 48.6% aqueous sodium hydroxide solution was added dropwise to the mixture at 65℃under reduced pressure (about 130 Torr) over 3 hours. During this time, the water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for 1 hour, and dehydration was performed. Thereafter, epichlorohydrin and diethylene glycol dimethyl ether were distilled off under reduced pressure, and after dissolution in 200mL of methyl isobutyl ketone, the resulting salt was removed by filtration. Thereafter, 0.4g of 48% aqueous sodium hydroxide solution was added thereto and reacted at 80℃for 2 hours. After the reaction, methyl isobutyl ketone was distilled off under reduced pressure as a solvent after filtration and washing with water to obtain 43g of an epoxy resin (epoxy resin C) which was a solid at ordinary temperature. The melting point of the obtained epoxy resin C was 139 ℃, the epoxy equivalent was 226g/eq, and the hydrolyzable chlorine was 80ppm.

Synthesis examples 1 to 4 (preparation of epoxy resin D)

Into a 1000ml four-necked flask, 77.5g of 4,4 '-dihydroxybiphenyl, 119.3g of diethylene glycol dimethyl ether and 41.8g of 4,4' -dichloromethyl biphenyl were charged, and the mixture was stirred under nitrogen flow and heated to 160℃to react for 20 hours to give a polyhydric hydroxyl resin having an OH equivalent of 135 g/eq. After completion of the reaction, 45.6g of diethylene glycol dimethyl ether was recovered, 455.1g of epichlorohydrin was added, and 70.5g of a 48% aqueous sodium hydroxide solution was added dropwise under reduced pressure (about 130 Torr) at 62℃over 4 hours. During this time, the water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for 1 hour. Thereafter, epichlorohydrin was distilled off, methyl isobutyl ketone was added thereto, and after removing salts by washing with water, filtration and washing with water were performed, followed by distillation under reduced pressure of methyl isobutyl ketone, whereby 129g of an epoxy resin (epoxy resin D) was obtained. The epoxy resin D had an epoxy equivalent of 200g/eq, a softening point of 125℃and a melting point of 120℃and a melt viscosity of 0.21 Pa.s, and a hydrolyzable chlorine of 230ppm.

Examples 1-1 to 1-9 and comparative examples 1-1 to 1-5

The epoxy resin obtained in Synthesis example 1-1 (epoxy resin A), the epoxy resin obtained in Synthesis example 1-2 (epoxy resin B), the epoxy resin obtained in Synthesis example 1-3 (epoxy resin C), and the epoxy resin obtained in Synthesis example 1-4 (epoxy resin D) were used as epoxy resins. 4,4' -dihydroxydiphenyl ether (curing agent A, OH equivalent 101 g/eq.) and phenol novolac (curing agent B: aica manufactured by industrial scale, BRG-557, OH equivalent 105g/eq., softening point 82 ℃) are used as curing agents, triphenylphosphine is used as curing accelerator, spherical alumina (manufactured by Denka, DAW-10, average particle size 12.2 μm) is used as inorganic filler, talc (additive A, average particle size 10-15 μm, fuji film and photo-purity chemical), mica (additive B, synthetic mica, fuji film and photo-purity chemical) are used as additives, and additive C (1, 3:2, 4-bis (3, 4-dimethylbenzylide) -D-sorbitol, tokyo formation industrial scale) or additive D (sodium 2,4,8, 10-tetra-tert-butyl-12H-dibenzo [ D, g ] [1,3,2] dioxaphosphorine (manufactured by industrial scale) -536-oxide are used as nucleating agents.

The components shown in Table 1 were mixed thoroughly in a mixer, and then kneaded with a heated roll for about 5 minutes, and the obtained products were cooled and pulverized to obtain epoxy resin compositions of examples 1-1 to 1-9 and comparative examples 1-1 to 1-5, respectively. After molding at 175℃for 5 minutes, the epoxy resin composition was post-cured at 180℃for 12 hours to obtain a cured molded article, and the physical properties of the cured molded article were evaluated. The results are summarized in Table 1. The numerals of the respective components in table 1 represent parts by weight.

[ Evaluation ]

(1) Thermal conductivity

The thermal conductivity was measured by a transient hot wire method using a type LFA447 thermal conductivity meter manufactured by NETZSCH.

(2) Melting Point and heat of fusion measurement (DSC method)

The sample was precisely weighed about 10mg using a type TG/DTA7300 differential scanning calorimeter (manufactured by HITACHI HIGH-TECH SCIENCE), and measured at a temperature increase rate of 10℃per minute under a nitrogen stream. When a cured product containing an inorganic filler is used as a sample, the heat of fusion is converted only into a resin component.

(3) Coefficient of linear expansion, glass transition temperature

The linear expansion coefficient and the glass transition temperature were measured at a temperature rise rate of 10℃per minute using a thermo-mechanical measuring apparatus type TMA7100 made by HITACHI HIGH-TECH SCIENCE.

(4) Water absorption rate

After post-curing, a disk having a diameter of 50mm and a thickness of 3mm was molded, and the weight change rate after moisture absorption at 85℃and a relative humidity of 85% was measured for 100 hours.

(5) XRD measurement and calculation of crystallinity

XRD measurement was performed using RINT TTR3 manufactured by Rigaku corporation. The measurement conditions were as follows. Diffraction angle 2 theta is 10-30 degrees, scanning speed is 0.25 degrees/min, divergence slit is 1/2 degrees, divergence vertical limit slit is 10mm, scattering slit is 1/2 degrees, and light receiving slit is 0.3mm.

The crystallinity is calculated by excluding diffraction peaks of talc observed in a region where 2θ is 28 ° to 29 °. When mica is used, peaks observed in the region of 6 ° to 8 ° are excluded. Here, the crystalline peak means a peak having a diffraction peak width of 5 ° or less, preferably 3 ° or less, that is, a sharp peak, and the amorphous peak means a broad peak having a diffraction peak width of 8 ° or more.

Crystallinity= [ crystalline peak area/(crystalline peak area+amorphous peak area) ] x 100

From these results, the epoxy resin composition obtained in examples is excellent in thermal conductivity and therefore suitable for power elements and vehicle-mounted applications. When the epoxy resin composition of comparative example containing no predetermined layered clay mineral was used, no crystalline peak was obtained and the crystallinity was 0% because it was an amorphous peak.

TABLE 1

[ Effect of the invention according to embodiment 1] industrial applicability

The epoxy resin composition exemplified in embodiment 1 provides a cured molded product excellent in moldability and reliability, high in thermal conductivity, low in water absorption, low in thermal expansion, high in heat resistance, and excellent in flame retardancy, and is suitable for use as an insulating material for electric and electronic materials such as semiconductor packages, laminated boards, heat dissipating substrates, and the like, and can exhibit excellent high heat dissipation, high heat resistance, flame retardancy, and high dimensional stability. The reason why such a specific effect is obtained is presumably because the layered clay mineral can improve the orientation of a specific cured epoxy resin having a rigid structure such as a biphenyl structure.

< Example of embodiment 2>

Embodiment 2 of the present invention will be described in further detail with reference to examples.

The measurement methods were each performed by the following methods.

1) OH equivalent (hydroxyl equivalent)

Using a potentiometric titration device, using 1, 4-bis-solventThe alkane was acetylated with 1.5mol/L acetyl chloride, the excess acetyl chloride was decomposed with water, and titration was performed using 0.5mol/L potassium hydroxide.

2) Vinyl equivalent

The sample was reacted with a West solution (iodine chloride solution), left in the dark, and thereafter, excess iodine chloride was reduced to iodine, and the iodine component was titrated with sodium thiosulfate to calculate the iodine value. The iodine value is converted to vinyl equivalent.

3) Total chlorine

1.0G of a sample was dissolved in 25ml of butyl carbitol, 25ml of 1N-KOH/propylene glycol solution was added thereto, and after 10 minutes of heating reflux, the mixture was cooled to room temperature, 100ml of 80% acetone/water was further added thereto, and potentiometric titration was performed with 0.002N-AgNO ₃ aqueous solution.

4) GPC measurement

A device comprising a main body (HLC-8220 GPC, manufactured by Tosoh Co., ltd.) and a column (TSKgel SuperMultiporeHZ-N4 pieces, manufactured by Tosoh Co., ltd.) connected in series was used, and the column temperature was 40 ℃. The eluent was Tetrahydrofuran (THF), and a flow rate of 0.35 mL/min was set, and a differential refractive index detector was used. The measurement sample was 50. Mu.L of a solution obtained by dissolving 0.1g of the sample in 10mL of THF and filtering the solution with a microfilter. The data were processed using GPC-8020 model II version 6.00 manufactured by Tosoh corporation.

5) Melting point, heat of fusion (DSC method)

About 10mg of a sample was precisely weighed by using a DSC7020 type differential scanning calorimeter (manufactured by HITACHI HIGH-TECH SCIENCE), and the measurement was performed under a nitrogen flow at a temperature rise rate of 10 ℃.

6) Solvent solubility (precipitation temperature)

2G of the resin and 1g of methyl ethyl ketone were weighed into a sample bottle, and after the mixture was heated and dissolved, the temperature was gradually lowered in a constant temperature bath, and the temperature in the bath where the resin was deposited was measured. The higher the precipitation temperature (°c), the poorer the solvent solubility.

7) Glass transition point (Tg)

Tg was obtained by a thermo-mechanical measuring apparatus (HITACHI HIGH-TECH SCIENCE, EXSTAR TMA/7100, manufactured by Kyowa Co., ltd.) under a temperature rising rate of 10℃per minute.

8) 5% Weight loss temperature (Td 5), carbon residue

The 5% weight loss temperature (Td 5) was measured under a nitrogen atmosphere at a temperature rise rate of 10℃per minute using a thermogravimetric/differential thermal analysis device (EXSTAR TG/DTA7300, manufactured by HITACHI HIGH-TECH SCIENCE). Further, the weight loss at 700 ℃ was measured, and the carbon residue was calculated.

9) Thermal conductivity

10 Dielectric constant and dielectric loss tangent)

Measured according to JIS C2138. The measurement frequency is represented by a value of 1 GHz.

11 Field desorption ionization mass spectrometry (FD-MS)

Measurement was performed using a mass spectrometer JMS-T100GCV (manufactured by Japanese electronics Co.). The sample was dissolved in acetone and supplied to the measurement.

Synthesis example 2-1

Into a 1000mL four-necked flask, 73.6g (0.60 mol) of 2, 5-xylenol (structural formula 2-14 below) was charged,

24.4G (0.20 mol) of p-hydroxybenzaldehyde (structural formula 2 to 15 below),

It was dissolved in 200.0g of 2-ethoxyethanol. After adding 20.0g of sulfuric acid while cooling in an ice bath, the mixture was heated at 100℃for 3 hours, and stirred to react. After the reaction, the obtained solution was subjected to reprecipitation with water, washing with water, filtration and vacuum drying, whereby 65.0g of a trifunctional hydroxy compound having a hydroxy equivalent of 118g/eq was obtained. The trifunctional hydroxy compound is a compound of formula (2-4) wherein R ¹～R⁴ is methyl and R ⁵ and R ⁶ are hydrogen atoms.

Next, 59.0g (0.17 mol) of the obtained trifunctional hydroxy compound, 400g of methyl ethyl ketone, 91.6g (0.60 mol) of chloromethylstyrene (structural formula 2-16 described below) were charged into a 1000ml four-necked flask,

The temperature was raised to 60℃and 33.7g of potassium hydroxide dissolved in 101g of methanol was added dropwise over 3 hours to react for a further 6 hours. After the completion of the reaction, the solvent was distilled off by filtration, reprecipitation was performed with methanol, washing with a large amount of water, and drying under reduced pressure was performed to obtain 102.4g of a vinyl resin (vinyl resin A). The basic structure of the vinyl resin A is that in the formula (2-1), R ¹～R⁴ is methyl, R ⁵ and R ⁶ are hydrogen, the vinyl equivalent is 225g/eq, the hydroxyl equivalent is 12000g/eq, the total chlorine is 600ppm, the melting point is 130 ℃, and Mn is 780.

GPC chart of the obtained vinyl resin A is shown in FIG. 3.

Synthesis example 2-2

Into a 1000ml four-necked flask, 65.3g (0.35 mol) of 4,4' -dihydroxybiphenyl (structural formula 2-17 shown below) was charged,

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

Under nitrogen flow, the reaction was carried out for 3 hours while stirring and then heated to 170℃and further reacted with (0.04 mol) of dihydroxydiphenylmethane (4, 4' -dihydroxydiphenylmethane (structural formula 2 to 19 below) in an amount of 36.2%, 2,4' -dihydroxydiphenylmethane: 46.6% and 2,2' -dihydroxydiphenylmethane: 17.2%) in an amount of 7.8g,

The polyhydric hydroxyl resin of the formula (2-7) was produced (hydroxyl equivalent 129 g/eq).

After the completion of the reaction, 50.7g of diethylene glycol dimethyl ether was recovered, 320g of methyl ethyl ketone and 135.5g of chloromethyl styrene were added thereto, the temperature was raised to 60℃and 49.8g of potassium hydroxide dissolved in 150g of methanol was added dropwise over 3 hours to react for a further 6 hours. After the completion of the reaction, the solvent was distilled off by filtration, reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 141g of vinyl resin (vinyl resin B) as a white solid of the formula (2-6) (i.e., the formula (2-2)). Vinyl resin B had a vinyl equivalent of 275g/eq, a hydroxyl equivalent of 15000g/eq, total chlorine of 300ppm, mn of 1330 and a melting point of 145 ℃. The basic structures of the polyhydroxyl resin and vinyl resin B are that in the formulas (2-6) and (2-7), A is-CH ₂ -group, the ratio (molar ratio) of e/(e+f) is 0.93, e is 4.2, and f is 0.3.

GPC chart of the obtained vinyl resin B is shown in FIG. 4.

Synthesis examples 2 to 3

Into a 2L four-necked separable flask, 74.5g (0.4 mol) of 4,4' -dihydroxybiphenyl and 18.4g (0.08 mol) of 1, 5-dibromopentane (structural formula 2-20 below) were charged,

After 500g of N-methyl-2-pyrrolidone was dissolved therein, 41.5g of potassium carbonate was added thereto, and the mixture was heated to 120℃under nitrogen flow with stirring. Thereafter, 20.6g (0.12 mol) of 2, 6-dichlorobenzonitrile (structural formula 2-21 below) was added,

The temperature was raised to 145℃and the reaction was carried out for 6 hours. 28.2g of acetic acid was added to the reaction mixture to neutralize the mixture, followed by distillation under reduced pressure to remove N-methyl-2-pyrrolidone. After 250mL of methyl isobutyl ketone was added to the reaction mixture to dissolve the product, the product was washed with water to remove the salt. Thereafter, methyl isobutyl ketone was removed by distillation under reduced pressure to obtain 72.6g of a hydroxy resin. The hydroxyl equivalent weight of the obtained hydroxyl resin was 225g/eq and Mn was 520. The p-value (average) was 2.3. The basic structure of the hydroxyl resin is that Y is a direct bond in the formula (2-13), and B has both a structural unit in the case of a benzonitrile structure and a structural unit in the case of- (CH ₂)_q - (q=5).

Next, 74.3g (0.33 mol) of the obtained hydroxy resin, 400g of methyl ethyl ketone, and 61.0g (0.40 mol) of chloromethylstyrene were charged into a 1000ml four-necked flask, the temperature was raised to 60℃and 22.4g (0.40 mol) of potassium hydroxide dissolved in 70g of methanol was added dropwise over 3 hours to react for a further 6 hours. After the completion of the reaction, the solvent was distilled off by filtration, reprecipitation was performed with methanol, washing with a large amount of water, and drying under reduced pressure was performed to obtain 84.3g (vinyl resin C) of vinyl resin of formula (2-12) (i.e., formula (2-3)). The vinyl resin C had a vinyl equivalent of 341g/eq, a hydroxyl equivalent of 10000g/eq, total chlorine of 900ppm, mn of 710 and a melting point of 174 ℃. The basic structure of the vinyl resin C is that in the formulas (2-12) and (2-3), q is 5, g is 1-3, h is 1-3, and p value (average value) is 1.8.

GPC chart of the obtained vinyl resin C is shown in FIG. 5, and FD-MS spectrum chart is shown in FIG. 6.

Synthesis examples 2 to 4

A1000 ml four-necked flask was charged with 40.8g of 4,4 '-bis (chloromethyl) biphenyl, 75.5g of 4,4' -dihydroxybiphenyl and 120g of diethylene glycol dimethyl ether, and the mixture was stirred under nitrogen flow and heated to 160℃to react for 10 hours. Then, the mixture was allowed to stand at 70℃and then, 280g of diethylene glycol dimethyl ether and 129.5g of chloromethyl styrene were added thereto, followed by dropwise addition of 100.0g of 48% potassium hydroxide, and the mixture was reacted, whereby it was confirmed by gas chromatography that no chloromethyl styrene remained, and the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, and then neutralized and washed with water to obtain a vinyl resin (vinyl resin D). The vinyl resin D obtained had a vinyl equivalent of 256g/eq, a hydroxyl equivalent of 1500g/eq, total chlorine of 1270ppm, mn of 1100 and a melting point of 210 ℃.

The melting point of the vinyl resin D is high, and is presumed as follows. That is, since dihydroxydiphenyl methane was not used as a raw material, the content of the biphenyl component was large as compared with synthetic example 2-2, or the melting point of the hydroxy resin obtained by inhibiting molecular movement due to the biphenyl structure was high. Thus, it is presumed that since the solvent solubility of the hydroxyl resin is relatively lowered, many unreacted hydroxyl groups (polar groups having hydrogen bonding properties) remain in the subsequent reaction with chloromethylstyrene, and that vinyl benzyl ether groups having flexibility are reduced.

Synthesis examples 2 to 5

Into a 1000ml four-necked flask, 50.0g of dihydroxydiphenyl methane (4, 4' -dihydroxydiphenyl methane: 36.2%, 2,4' -dihydroxydiphenyl methane: 46.6%, 2' -dihydroxydiphenyl methane: 17.2%), 400g of methyl ethyl ketone, 80.1g of chloromethyl styrene were charged, the temperature was raised to 60℃and 29.5g of potassium hydroxide dissolved in 88g of methanol was added dropwise over 3 hours to react for a further 6 hours. After the completion of the reaction, the solvent was distilled off by filtration, reprecipitation was performed with methanol, washing with a large amount of water, and drying under reduced pressure was performed to obtain 95.4g of a vinyl resin (vinyl resin E). The vinyl resin E had a vinyl equivalent of 217g/eq, a hydroxyl equivalent of 17000g/eq, total chlorine of 400ppm, mn of 440 and a melting point of 80 ℃.

The melting point of the vinyl resin E is low, and is presumed as follows. That is, unlike synthesis examples 2 to 4, since only dihydroxydiphenyl methane was used as a raw material to react with chloromethyl styrene, the melting point of the hydroxy resin obtained by not containing a biphenyl component was presumably lower than that of synthesis example 2 to 2.

Examples 2-1 to 2-5 and comparative examples 2-1 to 2-4

The vinyl resins A to E obtained in Synthesis examples 2-1 to 2-5 were used as vinyl resins, talc (additive A, average particle diameter: 10 to 15 μm, manufactured by Fuji photo-alignment Co., ltd.), PERBUTYL P (manufactured by Nippon Kabushiki Kaisha Co., ltd.), organic peroxide (manufactured by Nippon Kaisha Co., ltd.), ADK STAB AO-60 (manufactured by ADEKA Co., ltd.) as antioxidants, spherical alumina (manufactured by Denka Co., DAW-10, average particle diameter: 12.2 μm) as inorganic filler A, spherical silica (manufactured by Denka Co., FB-8S) as inorganic filler B, and the above were mixed in the mixing ratio shown in Table 1, and dissolved in a solvent to prepare uniform compositions. The composition was applied to a PET film and dried at 130 ℃ 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 while applying a pressure of 2MPa at 130 ℃ for 15 minutes and at 210 ℃ for 80 minutes under reduced pressure. The properties of the obtained cured product are shown in table 2.

The cured product formed from the vinyl resin composition of example has higher thermal conductivity and excellent physical properties such as low dielectric constant and low dielectric loss tangent than those of comparative example.

TABLE 2

[ Effect of the invention according to embodiment 2 ] industrial applicability

The vinyl resin composition exemplified in embodiment 2 is excellent in solvent solubility, and is suitable for use in applications such as lamination, molding, casting, and adhesion, and cured products thereof. The cured product is also excellent in heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy, and therefore is suitable for use in packaging of electric and electronic components, circuit board materials, and the like.

The vinyl resin composition and cured product of embodiment 2 of the present invention are useful as electronic materials for high-speed communication devices, and as materials that are easily dissipated heat generated from electronic components or wiring and have little signal loss.

Claims

1. A resin composition comprising at least a crystalline resin and an additive, wherein the additive is a layered clay mineral and comprises 1 to 20 parts by weight of the layered clay mineral per 100 parts by weight of the resin component,

2. The resin composition of claim 1, wherein the additive is talc or mica.

3. The resin composition of claim 2, wherein the additive is talc.

4. The resin composition according to claim 1, wherein the crystalline resin is an epoxy resin and/or a vinyl resin.

5. The resin composition according to claim 4, wherein the crystalline resin is an epoxy resin having a melting point of more than 80 ℃ and 180 ℃ or less and/or a vinyl resin having a melting point of 90 to 200 ℃.

6. The resin composition according to any one of claims 1 to 5, wherein the crystalline resin is an epoxy resin, the resin composition contains a curing agent, and a diffraction peak is detected in a region having a diffraction angle 2 θ of 15 ° or more and less than 25 ° in measurement of a cured product of the resin composition by an X-ray diffraction method (XRD).

7. The resin composition according to claim 6, wherein the epoxy resin is represented by the following general formula (1-1) or (1-2),

In the formula (1-1), G represents a glycidyl group, 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, n represents a number of 0 to 20,

In the formula (1-2), Y independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂-、-CO-、-COO-、-CONH-、-CH₂ -, or-C (CH ₃)₂ -, B independently represents a benzonitrile structure or- (CH ₂)_q -, p represents a number of 0 to 15), and q represents a number of 3 to 10.

8. The resin composition according to any one of claims 1 to 5, wherein the crystalline resin is a vinyl resin having a vinyl equivalent of 150 to 1000g/eq, a hydroxyl equivalent of 5000g/eq or more and a total chlorine content of 2000ppm or less.

9. The resin composition according to claim 8, wherein the vinyl resin is represented by any one or more of the following general formulae (2-1) to (2-3),

In the formula (2-1), R ¹～R⁶ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms,

In the 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, X independently represents a benzene ring, a naphthalene ring, or a biphenyl ring, n represents a number of 0 to 20,

In the formula (2-3), Y independently represents a single bond, an oxygen atom, a sulfur atom, -SO ₂-、-CO-、-COO-、-CONH-、-CH₂ -, or-C (CH ₃)₂ -, B independently represents a benzonitrile structure or- (CH ₂)_q -, p represents a number of 0 to 15), and q represents a number of 3 to 10).

10. The resin composition according to any one of claims 1 to 5, wherein the inorganic filler other than the layered clay mineral is contained in an amount of 20 to 90 wt%.

11. The resin composition according to any one of claims 1 to 5, which is a cured product for providing high heat conductivity.

12. The resin composition according to claim 6, wherein the resin composition is a cured product for high heat conductivity having a crystallinity of 10% or more.

13. A cured product obtained by curing the resin composition according to any one of claims 1 to 5.