TWI880069B - Curable resin composition, prepreg and cured product thereof - Google Patents

Abstract

The present invention provides a curable resin composition and a cured product thereof showing excellent heat resistance, copper foil peeling strength, dielectric properties, and moisture resistance. A curable resin composition comprises a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond, wherein the weight ratio of the component (A) to the component (B) is 50/50 to 5/95. (In formula (1), R represents a hydrogen atom or a methyl group. m represents an integer from 0 to 3. n is a repeating number, and its average value is 1<n<5.)

Description

Curable resin composition, prepreg and cured product thereof

The present invention relates to a curable resin composition, a prepreg and a cured product thereof, which can be preferably used in semiconductor sealing materials, printed wiring boards, electrical/electronic parts such as build-up laminates, lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and three-dimensional (3D) printing applications.

In recent years, multilayer boards with electrical/electronic components have been required to have a wide range of characteristics and advanced features due to the expansion of their application areas. For example, previously, semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing capabilities such as central processing units (CPUs) are mostly mounted on multilayer boards made of polymer materials. As the speed of components such as CPUs increases, the clock frequency increases, signal propagation delays or transmission losses become problems, and wiring boards are required to have low dielectric constants or low dielectric loss tangents.

In terms of the development of communication technology, the fifth generation (5G) of mobile communication is taking shape in recent years. It is expected that not only communication devices using Sub6, but also communication devices using quasi-millimeter waves and millimeter waves above 10GHz, especially above 28GHz, will increase explosively. In base stations, antennas, and communication devices, substrate materials corresponding to high frequencies are required. In these substrate materials, in order not to reduce the transmission speed, high dielectric properties (especially dielectric loss tangent) are emphasized, and materials that can be used stably in these areas are required.

In addition, in recent years, due to the popularity of mobile electronic devices such as mobile phones, precision electronic devices have begun to be carried outdoors or used very close to the human body, so they need to be resistant to the external environment (especially resistant to moisture and heat). Furthermore, in the automotive field, electrification is developing rapidly, and sometimes precision electronic devices are installed near the engine, which requires a higher level of heat and moisture resistance.

Wiring boards using BT resins, which are resins that use bisphenol A cyanate compounds and bismaleimide compounds together as in Patent Document 1, are widely used as high-performance wiring boards because of their excellent heat resistance, chemical resistance, and dielectric properties. However, improvements are required to achieve further high performance as described above.

In this case, the maleimide resin available on the market has greatly improved heat resistance compared to the epoxy resins used in the above applications, and exhibits excellent dielectric properties in the high-frequency region. However, the maleimide resin with high heat resistance has the following disadvantages: low moisture resistance, and because it is rigid and brittle, it also has low adhesion to copper foil.

In contrast, maleimide resins such as those in Patent Document 2 and Patent Document 3 have also been developed, but they are not yet sufficient.

In addition, a composition including a maleimide resin and an acrylic-containing phenol resin is proposed as in Patent Document 4, but the phenolic hydroxyl groups that do not participate in the reaction will remain during the curing reaction, so in addition to insufficient dielectric properties, there is also a problem of high water absorption.

[Prior art literature] [Patent Literature]

[Patent document 1] Japanese Patent Publication No. 54-30440

[Patent document 2] Japanese Patent Publication No. 3-100016

[Patent Document 3] Japanese Patent Publication No. 5030297

[Patent document 4] Japanese Patent Publication No. 04-359911

[Patent document 5] Japanese Patent Publication No. 4-75222

[Patent Document 6] Japanese Patent Publication No. 6-37465

The present invention is made in view of this situation, and its purpose is to provide a curable resin composition and its cured product that exhibit excellent heat resistance, copper foil peeling strength, dielectric properties, and moisture resistance.

The inventors of the present invention have made great efforts to solve the above problems and found that the cured product of the curable resin composition containing a maleimide compound with a specific structure and a polyphenylene ether compound with an unsaturated double bond has excellent heat resistance, copper foil peeling strength, dielectric properties, and moisture resistance, thereby completing the present invention.

That is, the present invention relates to the following [1]~[7].

[1]

A curable resin composition contains a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond, wherein the weight ratio of component (A) to component (B) is 50/50 to 5/95.

[Chemistry 1]

(In formula (1), R represents a hydrogen atom or a methyl group. m represents an integer from 0 to 3. n is a repetition number, and its average value is 1<n<5.)

[2]

A curable resin composition contains a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond, wherein the amount of component (B) is 0.20 equivalents to 4.2 equivalents per 1 equivalent of component (A).

(In formula (1), R represents a hydrogen atom or a methyl group. m represents an integer from 0 to 3. n is a repetition number, and its average value is 1<n<5.)

[3]

The curable resin composition as described in the above item [1] or [2], wherein the component (B) is a polyphenylene ether compound having a (meth)acrylic group.

[4]

The curable resin composition as described in any one of the above items [1] to [3], wherein the component (B) is a compound represented by the following formula (2) or a compound represented by the following formula (4).

(In formula (2), n is the number of repetitions, and its average value is 1<n<10.)

(In formula (4), n is the number of repetitions, and its average value is 1<n<10.)

[5]

The hardening resin composition as described in any one of the preceding items [1] to [4] further contains a hardening accelerator.

[6]

A prepreg, wherein the curable resin composition as described in any one of the above items [1] to [5] is retained in a sheet-like fiber substrate.

[7]

A cured product obtained by curing the curable resin composition described in any one of the preceding items [1] to [5], or the prepreg described in the preceding item [6].

The cured product of the curable resin composition of the present invention has excellent heat resistance, copper foil peeling strength, dielectric properties, and moisture resistance.

Figure 1 is a gel permeation chromatography (GPC) diagram of Synthesis Example 1.

Figure 2 is the GPC chart of Synthesis Example 2.

The curable resin composition of the present invention is described below.

The curable resin composition of the present invention contains a maleimide compound represented by the following formula (1) (hereinafter, also referred to as component (A)) and a polyphenylene ether compound having an unsaturated double bond (hereinafter, also referred to as component (B)).

(In formula (1), R represents a hydrogen atom or a methyl group. m represents an integer from 0 to 3. n is a repeating number, and its average value is 1<n<5)

The compound represented by the formula (1) is particularly preferably represented by the following formula (1-a).

[Chemistry 6]

In the above formula (1), the value of n can be calculated from the value of the number average molecular weight obtained by measuring the maleimide resin by gel permeation chromatography (GPC, detector: RI (refractive index)), or the area ratio of each separated peak.

In the above formula (1), when n=1, the solubility in the solvent is low. In addition, when n is 5 or more, the fluidity during molding deteriorates and the properties as a cured product cannot be fully exerted.

Component (A) preferably has a molecular weight distribution, and in the formula (1), the content of n=1 body obtained by GPC analysis (RI) is preferably 98% by area or less, more preferably 20% by area to 90% by area, further preferably 30% by area to 80% by area, and particularly preferably 40% by area to 80% by area. If the content of n=1 body is 98% by area or less, the heat resistance becomes good. In addition, the crystallinity is reduced and the solvent solubility becomes good. On the other hand, if the lower limit of the n=1 body is 20% by area or more, the viscosity of the resin solution is reduced and the impregnation becomes good. In addition, when the solid is taken out, the solvent can be removed at a low temperature, so self-polymerization is not easy to occur, and the operation becomes easy.

Component (A) has good solvent solubility by increasing the proportion of asymmetric structures with different orientations relative to the maleimide group, and can also improve dielectric properties in its cured product. The orientation ratio in the n=1 body of formula (1) can be determined by high performance liquid chromatography (HPLC) analysis (225nm), and the ortho-para body is preferably 30% by area and less than 60% by area in the total amount of the n=1 body, more preferably 35% by area and less than 55% by area, and particularly preferably 40% by area and less than 55% by area.

The softening point of component (A) is preferably 50°C to 150°C, more preferably 80°C to 120°C, further preferably 90°C to 120°C, and particularly preferably 95°C to 120°C. In addition, the melt viscosity at 150°C is 0.05Pa.s to 100Pa.s, preferably 0.1Pa.s to 40Pa.s.

The following describes the method for producing component (A), but is not limited to this method.

[Method for producing aromatic amine resin]

Component (A) can use an aromatic amine resin represented by the following formula (3) as a precursor.

(In formula (3), R represents a hydrogen atom or a methyl group. m represents an integer from 0 to 3. n is a repetition number, and its average value is 1<n<5.)

The method for preparing the aromatic amine resin represented by the formula (3) is not particularly limited. For example, in Patent Document 5, aniline is reacted with m-diisopropenylbenzene or m-di(α-hydroxyisopropyl)benzene in the presence of an acidic catalyst at 180°C to 250°C to obtain the n=1 isomer in the formula (3) as the main component. The n=1 isomer includes compounds with symmetrical structures having the same orientation relative to two aniline molecules, such as 1,3-bis(p-aminocumyl)benzene and 1,3-bis(oxamidocumyl)benzene; and three isomers of compounds with asymmetrical structures having different orientation relative to two aniline molecules, such as 1-(oxamidocumyl)-3-(p-aminocumyl)benzene. Furthermore, n=2~5 isomers are also generated as byproducts, but in Patent Document 5, these are purified by crystallization to obtain 1,3-bis(p-aminocumyl)benzene with a purity of 98%. In Patent Document 6, 1,3-bis(p-aminocumyl)benzene is subjected to maleimidation to synthesize N,N'-(1,3-phenylene-di-(2,2-propylene)-di-p-phenylene)bismaleimide, and a crystalline product is obtained, but heating is required to dissolve it in a solvent, and if it is left at room temperature after heating, crystals are precipitated within a few hours. Therefore, when the resin composition is adjusted, there is a possibility of crystallization. The higher the concentration of N,N'-(1,3-phenylene-di-(2,2-propylene)-di-p-phenylene) bismaleimide, the higher the possibility of crystallization. In order to make printed wiring boards or composite materials, glass cloth or carbon fiber is impregnated with varnish and the resin is attached. If crystals precipitate, the impregnation operation cannot be carried out. On the other hand, if the temperature is increased to maintain the dissolved state, the reaction of the composition will be accelerated, and the usable time of the varnish will be shortened.

When synthesizing the aromatic amine resin represented by the formula (3), the acidic catalyst used may include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid and the like. In the present invention, protonic acids such as hydrochloric acid, p-toluenesulfonic acid, and methanesulfonic acid are preferred. These may be used alone or in combination of two or more. The amount of the catalyst used is preferably 1% to 12% by weight, more preferably 1% to 10% by weight, and particularly preferably 1% to 7% by weight relative to 100% by weight of the aniline used. If it is more than 12% by weight, the target asymmetric structure compound is less, and the compound with a symmetric structure is formed preferentially. On the other hand, if it is less than 1%, not only will the reaction proceed more slowly, but there is also a possibility that the reaction cannot be completed, so it is not good.

The reaction can be carried out using an organic solvent such as toluene or xylene as required, or can be carried out without a solvent. For example, after adding an acidic catalyst to a mixed solution of aniline and a solvent, when the catalyst contains water, it is preferred to remove the water from the system by azeotropy. Then, diisopropenylbenzene or di(α-hydroxyisopropyl)benzene is added, and then the temperature is raised while removing the solvent from the system, and the reaction is carried out at 140°C to 190°C, preferably 160°C to 190°C, for 5 hours to 50 hours, preferably 5 hours to 30 hours. When the reaction temperature is too high, rebonding will occur after the asymmetric structure is generated, and the symmetric structure will be formed first, so the target solvent solubility and electrical properties cannot be exerted. When using di(α-hydroxyisopropyl)benzene, water is produced as a by-product, so it is removed from the system while azeotroping with the solvent when the temperature is raised. After the reaction is completed, the acidic catalyst is neutralized with an alkaline aqueous solution, and a non-water-soluble organic solvent is added to the oil layer. The waste water is repeatedly washed with water until it becomes neutral, and then the solvent and excess aniline derivatives are removed under heating and reduced pressure. When using activated clay or ion exchange resin, the reaction liquid is filtered after the reaction is completed to remove the catalyst.

In addition, diphenylamine may be produced as a by-product depending on the reaction temperature or the type of catalyst, so it is better to remove it as needed. Under high temperature/high vacuum, or by using water vapor distillation, the diphenylamine derivative is removed to less than 1% by weight, preferably less than 0.5% by weight, and more preferably less than 0.2% by weight.

[Maleimide resin production method]

Component (A) can be obtained by subjecting the aromatic amine resin represented by the formula (3) obtained by the above steps to addition or dehydration condensation reaction with maleic acid or maleic anhydride (hereinafter also referred to as "maleic acid anhydride") in the presence of a solvent and a catalyst.

The solvent used in the reaction needs to remove the water generated in the reaction from the system, so it is better to use a water-insoluble solvent. For example, it can be listed as: aromatic solvents such as toluene and xylene; aliphatic solvents such as cyclohexane and n-hexane; ethers such as diethyl ether and diisopropyl ether; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl isobutyl ketone and cyclopentanone, etc., but it is not limited to these, and two or more solvents can be used in combination.

In addition to the above-mentioned non-water-soluble solvents, non-protonic polar solvents can also be used in combination. For example, dimethyl sulfone, dimethyl sulfone, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, etc. can be listed, and two or more can also be used in combination. When using non-protonic polar solvents, it is better to use one with a higher boiling point than the non-water-soluble solvent used in combination.

In addition, the catalyst used in the reaction is an acidic catalyst, which is not particularly limited, and examples thereof include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, phosphoric acid, etc. The amount of the acid catalyst used is generally 0.1% to 10% by weight relative to the aromatic amine resin, preferably 1% to 5% by weight.

For example, the aromatic amine resin represented by the formula (3) is dissolved in toluene and N-methyl-2-pyrrolidone, anhydrous maleic acid is added thereto to generate acylamine, and then p-toluenesulfonic acid is added to carry out the reaction while removing the water generated under reflux conditions from the system.

Alternatively, maleic acid anhydride is dissolved in toluene, and the N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the formula (3) is added under stirring to generate acylamine, and then p-toluenesulfonic acid is added to react while removing the water generated under reflux conditions from the system.

Alternatively, maleic acid anhydride is dissolved in toluene, p-toluenesulfonic acid is added, and the N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the formula (3) is added dropwise under stirring/reflux, while the water generated during the azeotropic reaction is removed from the system midway, and the reaction is carried out while toluene is returned to the system (the above is the first stage reaction).

In any method, maleic acid anhydrate is usually used in an amount of 1.0 to 3.0 equivalents, preferably 1.2 to 2.0 equivalents, relative to the amine group of the aromatic amine resin represented by formula (3).

In order to reduce the unclosed acylamine, water is added to the reaction solution after the maleimidation reaction listed above to separate it into a resin solution layer and a water layer. Since the excess maleic acid or maleic anhydride, aprotic polar solvent, catalyst, etc. are dissolved on the water layer side, they are separated and removed. The same operation is repeated to completely remove the excess maleic acid or maleic anhydride, aprotic polar solvent, and catalyst. The catalyst is added again to the maleimide resin solution of the organic layer from which the excess maleic acid or maleic anhydride, the aprotic polar solvent, and the catalyst have been removed, and the residual acylamine is subjected to a dehydration ring-closing reaction under heating and reflux conditions again, thereby obtaining a maleimide resin solution with a low acid value (the above is the second stage reaction).

The time for the dehydration closed-loop reaction is usually 1 to 5 hours, preferably 1 to 3 hours, and the aprotic polar solvent may be added as needed. After the reaction is completed, cool and wash repeatedly with water until the washing water becomes neutral. Then, after removing water by azeotropic dehydration under heating and reduced pressure, the solvent can be distilled off, or other solvents can be added to adjust the resin solution to the desired concentration. The solvent can also be completely distilled off and taken out in the form of solid resin.

Next, component (B) will be explained.

Component (B) is not particularly limited as long as it has an unsaturated double bond and a polyphenylene ether structure. Examples of unsaturated double bonds in component (B) include: (meth)acrylic acid, styryl, allyl, vinyl, and methallyl, preferably (meth)acrylic acid. Commercially available products include SA-9000-111 represented by the following formula (2) (manufactured by Saudi Basic Industries Corporation (Sabic), a polyphenylene ether compound having a methacrylate group) or OPE-2St 1200 represented by the following formula (4) (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styryl group). In particular, from the perspective of dielectric properties, the compound represented by the following formula (2) is preferred.

(In formula (2), n is the number of repetitions, and its average value is 1<n<10)

[Chemistry 9]

(In formula (4), n is the number of repetitions, and its average value is 1<n<10)

The weight average molecular weight (Mw) of component (B) is preferably 500-5000, more preferably 2000-5000, and further preferably 2000-4000. If the molecular weight is 500 or more, the heat resistance of the cured product is improved. If the molecular weight is 5000 or less, the melt viscosity is reduced, sufficient fluidity can be obtained, and the formability is good. In addition, due to the improved reactivity, the curing time can be shortened, and the heat resistance of the cured product is also improved. Specifically, the weight average molecular weight can be measured using gel permeation chromatography, etc.

Regarding component (B), free radical polymerizability can be imparted by reacting the polyphenylene ether compound with a compound having an unsaturated double bond such as methacrylic chloride, acrylyl chloride, chloromethylstyrene, etc.

The polyphenylene ether compound can be obtained by polymerization reaction or by subjecting a high molecular weight polyphenylene ether compound with a weight average molecular weight of 10,000 to 30,000 to a redistribution reaction. The redistribution reaction is, for example, heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a free radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by the redistribution reaction is preferably preferred because it has a hydroxyl group derived from a phenolic compound at both ends of the molecular chain that helps hardening. In addition, in terms of showing excellent fluidity, the polyphenylene ether compound obtained by polymerization reaction is preferred.

In the case of a polyphenylene ether compound obtained by a polymerization reaction, the molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc. In addition, in the case of a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it can be considered to adjust the amount of the phenolic compound used in the redistribution reaction, etc. That is, the greater the amount of the phenolic compound, the lower the molecular weight of the obtained component polyphenylene ether compound.

In addition, the polyphenylene ether compound specifically includes poly(2,6-dimethyl-1,4-phenylene oxide) and the like. That is, in the case of component (B) obtained by redistribution reaction, as a high molecular weight polyphenylene ether compound, a polyphenylene ether compound obtained by using poly(2,6-dimethyl-1,4-phenylene oxide) and the like can be listed. In addition, the phenolic compound used in the redistribution reaction is not particularly limited. For example, a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule such as bisphenol A, phenol novolac, cresol novolac, etc. can be preferably used. These can be used alone or in combination of two or more.

The weight ratio of component (A) to component (B) in the curable resin composition of the present invention is preferably 50/50 to 5/95, more preferably 30/70 to 5/95, further preferably 25/75 to 5/95, and particularly preferably 25/75 to 10/90. In addition, as the functional group equivalent ratio of component (A) to component (B), component (B) is preferably 0.2 equivalents to 4.2 equivalents, more preferably 0.5 equivalents to 4.2 equivalents, further preferably 0.7 equivalents to 4.2 equivalents, and particularly preferably 0.7 equivalents to 2.0 equivalents per 1 equivalent of component (A). When the component (B) is less than 0.2 equivalents, the maleimide group increases and the water absorption property deteriorates, and the hardened material becomes brittle, so the peeling strength of the copper foil decreases. On the other hand, when the component (B) is more than 4.2 equivalents, the crosslinking density decreases and the heat resistance deteriorates.

In the curable resin composition of the present invention, in addition to component (A) and component (B), any known resin material can also be used. Specifically, the following can be cited: phenol resin, epoxy resin, amine resin, active olefin-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate resin, acrylic resin, methallyl resin, active ester resin, etc., and one or more of them can be used. In addition, maleimide compounds other than component (A) can also be used in combination.

As phenol resins, epoxy resins, amine resins, active olefin-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate resins, and active ester resins, the resins listed below can be used, but are not limited thereto.

Phenolic resins: condensation products of phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthols, dihydroxybenzenes, alkyl-substituted dihydroxybenzenes, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.); condensation products of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, diisocyanate ... Polymers of vinyl biphenyl, diisopropyl biphenyl, butadiene, isoprene, etc.); condensation products of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); phenolic resins obtained by condensation of phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.); condensation products of bisphenols and various aldehydes; polyphenylene ether.

Epoxy resin: the above-mentioned phenol resin; glycidyl ether epoxy resin obtained by glycidylating alcohols, etc.; aliphatic epoxy resin represented by 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, etc.; glycidylamine epoxy resin represented by tetraglycidyl diamino diphenylmethane (TGDDM) or triglycidyl-p-aminophenol, etc.; glycidyl ester epoxy resin.

Amine resin: diaminodiphenylmethane; diaminodiphenylsulfone; isophoronediamine; naphthalenediamine; aniline novolac; o-ethylaniline novolac; aniline resin obtained by the reaction of aniline and xylylene chloride; amine resin obtained by the reaction of aniline described in Japanese Patent No. 6429862 with substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.).

Resins containing active olefins: condensation products of the phenolic resins and halogen compounds containing active olefins (chloromethylstyrene, allyl chloride, methylallyl chloride, acrylyl chloride, etc.); condensation products of phenols containing active olefins (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.). chloride), etc.); condensation products of epoxy resins or alcohols and substituted or unsubstituted acrylic esters (acrylates, methacrylates, etc.); maleimide resins (4,4'-diphenylmethane dimaleimide, polyphenylmethane maleimide, metaphenylene dimaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl 〕Propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane dimaleimide, 4-methyl-1,3-phenylene dimaleimide, 4,4'-diphenyl ether dimaleimide, 4,4'-diphenylsulfone dimaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene).

Isocyanate resins: aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, etc.; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, etc. Aliphatic or alicyclic diisocyanates such as isocyanate, hydroxylene diisocyanate, norbornene diisocyanate, lysine diisocyanate, etc.; polyisocyanates such as biuret forms of one or more isocyanate monomers or isocyanate forms obtained by trimerization of the above diisocyanate compounds; polyisocyanates obtained by urea formation reaction of the above isocyanate compounds with polyol compounds.

Polyamide resin: selected from amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.), lactamides (ε-caprolactam, ω-undecane lactamide, ω-laurolactam) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, etc.); cyclohexanediamine A polymer with one or more of a mixture of hexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, etc. alicyclic diamines; aromatic diamines such as xylene diamine, etc.) and dicarboxylic acids (aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc.; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfonate isophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, etc.; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; dialkyl esters and dichlorides of these dicarboxylic acids) as the main raw materials.

Polyimide resin: the diamine and tetracarboxylic acid dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic acid dianhydride, 1,2,3,4-benzene tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 3, 3',4,4'-diphenylsulfonate tetracarboxylic dianhydride, 2,2',3,3'-biphenylate tetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2'-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic diphthalic acid dianhydride, 1,5-pentamethylene-4,4'-diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic acid dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic acid dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl) -2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dihydride anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-biscyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4 ,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1 S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride) condensation product.

Cyanate resin: a cyanate compound obtained by reacting a phenol resin with a cyanide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanonaphthalene, dicyanobiphenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane , 2,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4-cyanophenyl)hexafluoropropane, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)sulfide, phenol novolac cyanate, and those obtained by converting the hydroxyl group of phenol-dicyclopentadiene copolymer into cyanate group, but are not limited to these.

In addition, the cyanate compound whose synthesis method is described in Japanese Patent Publication No. 2005-264154 is particularly preferred as a cyanate compound due to its low hygroscopicity, flame retardancy, and excellent dielectric properties.

In order to trimerize the cyanate group to form a sym-triazine ring as needed, the cyanate resin may also contain a catalyst such as zinc cycloalkanoate, cobalt cycloalkanoate, copper cycloalkanoate, lead cycloalkanoate, zinc octanoate, tin octanoate, lead acetylacetonate, dibutyltin maleate, etc. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.0001 to 0.0015 parts by mass, relative to 100 parts by mass of the total mass of the curable resin composition.

Active ester resin: A compound having one or more active ester groups in one molecule can be used as a hardener for hardening resins such as epoxy resins as needed. As active ester hardeners, preferred are compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. The active ester hardener is preferably obtained by a condensation reaction of at least one of a carboxylic acid compound and a thiocarboxylic acid compound with at least one of a hydroxyl compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound is preferred.

Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, phenoxyphenol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene.

As preferred specific examples of active ester curing agents, there can be listed active ester compounds containing dicyclopentadiene diphenol structure, active ester compounds containing naphthalene structure, active ester compounds containing acetylated products of phenol novolac, and active ester compounds containing benzoylated products of phenol novolac. Among them, active ester compounds containing naphthalene structure and active ester compounds containing dicyclopentadiene diphenol structure are more preferred. The so-called "dicyclopentadiene diphenol structure" means a divalent structural unit containing phenylene-dicyclopentylene-phenylene.

Examples of commercially available active ester curing agents include: "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure; and "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure. ; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing acetylated phenol novolac; "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing benzoylated phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester hardener of acetylated phenol novolac; "EXB-9050L-62M" manufactured by DIC Corporation as an active ester hardener containing phosphorus atoms, etc.

The curable resin composition of the present invention may further be used in combination with a curing accelerator (curing catalyst) to improve the curability. As a specific example of the curing accelerator that can be used, it is preferred to use a radical polymerization initiator for the purpose of promoting the self-polymerization of a curable resin capable of free radical polymerization such as an olefin resin or a maleimide resin or free radical polymerization with other components. As free radical polymerization initiators, there can be listed: ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzoyl peroxide; dialkyl peroxides such as dicumyl peroxide and 1,3-bis(tert-butylperoxyisopropyl)benzene; peroxyketal such as tert-butyl peroxybenzoate and 1,1-di-tert-butylperoxycyclohexane; α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-3,5,5-trimethyl The present invention also includes alkyl peroxyesters such as hexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, and t-amyl peroxybenzoate; peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane; organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, t-butylperoxyoctanoate, and lauryl peroxide; or azo compounds such as azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile), which are known curing accelerators, but are not particularly limited to these. Preferred are ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxyesters, peroxycarbonates, etc., and more preferred are dialkyl peroxides. The amount of free radical polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the curable resin composition. If the amount of free radical polymerization initiator used is large, the dielectric properties of the cured product will deteriorate.

The curable resin composition of the present invention may be added with or used in combination with a curing accelerator other than a free radical polymerization initiator as needed. Specific examples of curing accelerators that can be used include: tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diazo-bicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethylammonium hydroxide; triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutylammonium salt, triphenylphosphon ... Quaternary phosphonium salts such as phosphonium salts (the counter ions of the quaternary salts are halogens, organic acid radical ions, hydroxide ions, etc., without particular designation, and organic acid radical ions and hydroxide ions are particularly preferred.), tin octanoate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristicate) or zinc phosphates (octyl zinc phosphate, stearyl zinc phosphate, etc.) and other zinc compounds such as transition metal compounds (transition metal salts). Regarding the amount of the hardening accelerator, 0.01 to 5.0 parts by weight can be used as needed relative to 100 parts by weight of the hardening resin composition.

Furthermore, the curable resin composition of the present invention may also contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include: trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tri(xylyl)phosphate, tolyl diphenyl phosphate, tolyl-2,6-di(xylyl)phosphate, 1,3-phenylene bis(xylyl)phosphate, 1,4-phenylene bis(xylyl)phosphate, 4,4'-biphenylene(xylyl)phosphate) and other phosphates; 9,10-dihydro-9-oxo-10-phosphophananthrene-10-oxide, 10- Phosphanes such as (2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxides obtained by reacting epoxy resins with active hydrogen of the phosphanes, red phosphorus, etc., preferably phosphates, phosphanes or phosphorus-containing epoxides, particularly preferably 1,3-phenylenebis(di(xylyl)phosphate), 1,4-phenylenebis(di(xylyl)phosphate), 4,4'-biphenylene(di(xylyl)phosphate) or phosphorus-containing epoxides. The content of the phosphorus-containing compound is preferably in the range of 0.1 to 0.6 (weight ratio) of (phosphorus-containing compound)/resin component in the curable resin composition. If it is below 0.1, the flame retardancy is insufficient, and if it is above 0.6, there is a risk of adversely affecting the moisture absorption and dielectric properties of the cured product.

Furthermore, a light stabilizer may be added to the curable resin composition of the present invention as needed. As the light stabilizer, a hindered amine light stabilizer is preferred, and a hindered amine light stabilizer (HALS) is particularly preferred. HALS is not particularly limited, and typical examples include: condensation product of dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, condensation product of dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidinyl succinate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2 ,6,6-tetramethyl-4-piperidinyl)imino}〕, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)〔{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl〕butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidinyl)ester, etc. HALS can be used alone or in combination of two or more.

Furthermore, in the curable resin composition of the present invention, an adhesive resin may be formulated as needed. Examples of the adhesive resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, nitrile butadiene rubber (NBR)-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, silicone resins, etc., but are not limited thereto. The amount of adhesive resin is preferably within a range that does not damage the flame retardancy and heat resistance of the cured product, preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, relative to 100 parts by mass of the resin component.

Furthermore, in the curable resin composition of the present invention, powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconium oxide, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide, asbestos, glass powder, etc., or inorganic fillers such as these in spherical or crushed forms may be added as needed. In addition, in particular, when obtaining a curable resin composition for semiconductor packaging, the amount of the inorganic filler used in the curable resin composition is generally in the range of 80% to 92% by mass, preferably 83% to 90% by mass.

Furthermore, in the curable resin composition of the present invention, known additives can be formulated as needed. Specific examples of usable additives include polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, surface treatment agents for fillers such as silane coupling agents, mold release agents, carbon black, phthalocyanine blue, phthalocyanine green and other coloring agents. The amount of these additives formulated is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, relative to 100 parts by mass of the resin component.

The curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components in a prescribed ratio, usually pre-curing at 130°C to 180°C for 30 seconds to 500 seconds, and then post-curing at 150°C to 200°C for 2 hours to 15 hours, thereby performing a sufficient curing reaction to obtain the cured product of the present invention. In addition, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, etc., and cured after removing the solvent.

The hardening resin composition of the present invention obtained in this way has moisture resistance, heat resistance, high adhesion, low dielectric constant, and low dielectric loss tangent. Therefore, the hardening resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance, high adhesion, low dielectric constant, and low dielectric loss tangent. Specifically, it can be effectively used as insulating materials, laminated boards (printed wiring boards, ball grid array (BGA) substrates, build-up substrates, etc.), sealing materials, anti-corrosion agents, and other materials for all electrical/electronic parts. In addition, in addition to molding materials and composite materials, it can also be used in coating materials, adhesives, 3D printing, and other fields. In particular, in semiconductor sealing, solder reflow resistance is beneficial.

The semiconductor device is sealed with the curable resin composition of the present invention. Examples of the semiconductor device include dual in-line package (DIP), quad flat package (QFP), ball grid array (BGA), chip size package (CSP), small outline package (SOP), thin small outline package (TSOP), thin quad flat package (TQFP), etc.

The preparation method of the curable resin composition of the present invention is not particularly limited, and the curable resin composition can be prepared by dispersing or dissolving the components in a solvent or the like and uniformly mixing them, and removing the solvent by distillation as required, as described above, or by prepolymerization. For example, the prepolymerization can be carried out by heating the components (A) and (B) in the presence or absence of a catalyst, in the presence or absence of a solvent. Similarly, in addition to the components (A) and (B), curing agents such as epoxy resins, amine compounds, maleimide compounds, cyanate compounds, phenolic resins, acid anhydride compounds, and other additives can be added to carry out prepolymerization. For mixing or prepolymerization of the components, an extruder, kneader, roller, etc. are used when no solvent is present, and a reaction kettle with a stirring device is used when a solvent is present.

As a method of uniformly mixing without using a solvent, the mixture is mixed by fusion at a temperature in the range of 50°C to 100°C using a kneader, a roll, a planetary mixer, or the like, to produce a uniform curable resin composition. The obtained curable resin composition can also be crushed and then molded into a cylindrical tablet using a molding machine such as a tablet press, or into a granular powder or a powdery molded body, or the composition can be melted on a surface support and molded into a sheet with a thickness of 0.05mm to 10mm to produce a curable resin composition molded body. The obtained molded body is non-sticky at 0°C to 20°C, and the fluidity and curability are hardly reduced even if stored at -25°C to 0°C for more than 1 week.

The obtained molded body can be molded into a hardened product using a transfer molding machine or a compression molding machine.

An organic solvent may be added to the curable resin composition of the present invention to prepare a varnish-like composition (hereinafter, also referred to as varnish). The curable resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to prepare a varnish, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heated and dried, and the obtained prepreg is hot-pressed to prepare a cured product of the curable resin composition of the present invention. At this time, the solvent used in the mixture of the curable resin composition of the present invention and the solvent usually accounts for 10% to 70% by weight, preferably 15% to 70% by weight. If the amount of solvent is less than this range, the viscosity of the varnish becomes high and the workability deteriorates. If the amount of solvent is large, it becomes a cause of voids in the cured product. In addition, if it is a liquid composition, a cured resin containing carbon fibers can also be directly obtained by, for example, resin transfer molding (RTM).

In addition, the curable composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used in situations where the flexibility of the B-stage is improved. This film-type resin composition is obtained by making the curable resin composition of the present invention into the curable resin composition varnish and applying it on a peeling film, removing the solvent under heating, and then performing B-stage, thereby obtaining it as a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer of a multi-layer substrate, etc.

The curable resin composition of the present invention can be heated to melt, reduce viscosity, and be impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, and inorganic fibers other than glass or polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by Dupont Co., Ltd.), wholly aromatic polyamide, polyester; and organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fiber, but are not particularly limited to these. The shape of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, roving, chopped strand mats, etc. In addition, as a weaving method for woven fabrics, there are known plain weaves, basket weaves, twill weaves, etc., which can be appropriately selected from these known weaving methods according to the target use or performance. In addition, it is preferred to use a glass fabric that has been subjected to fiber opening treatment or surface treatment using a silane coupling agent. The thickness of the substrate is not particularly limited, and is preferably about 0.01mm to 0.4mm. In addition, a prepreg can also be obtained by impregnating the varnish in the reinforcing fiber and heating and drying it.

The laminated plate of the present embodiment includes one or more of the prepregs. The laminated plate is not particularly limited as long as it includes one or more prepregs, and may have any other layers. As a method for manufacturing the laminated plate, generally known methods can be appropriately applied without particular limitation. For example, when forming a laminated plate with a metal foil, a multi-stage pressing machine, a multi-stage vacuum pressing machine, a continuous forming machine, an autoclave forming machine, etc. can be used, and the laminated plate can be obtained by stacking the prepregs on each other and performing heating and pressure forming. At this time, the heating temperature is not particularly limited, and is preferably 65°C to 300°C, and more preferably 120°C to 270°C. In addition, the pressure of pressurization is not particularly limited. If the pressure is too large, it is difficult to adjust the solid content of the resin of the laminate, and the quality is unstable. If the pressure is too small, bubbles or the adhesion between the layers will deteriorate. Therefore, it is preferably 2.0MPa~5.0MPa, and more preferably 2.5MPa~4.0MPa. The laminate of this embodiment can be preferably used as a laminate with metal foil described later by including a layer with metal foil.

The prepreg is cut into the desired shape, laminated with copper foil etc. as needed, and then the laminate is subjected to pressure by press forming, autoclave forming, sheet winding forming, etc., while the curable resin composition is heated and cured, thereby obtaining a laminated board (printed wiring board) or carbon fiber reinforced material for electrical and electronic use.

The cured product of the present invention can be used for various purposes such as molding materials, adhesives, composite materials, coatings, etc. The cured product of the curable resin composition described in the present invention shows excellent heat resistance and dielectric properties, and can therefore be preferably used in sealing materials for semiconductor elements, sealing materials for liquid crystal display elements, sealing materials for organic electroluminescence (EL) elements, printed wiring boards, build-up laminates and other electrical and electronic parts or composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

[Implementation example]

The present invention is described in detail below by way of examples and comparative examples. In addition, "parts" and "%" herein represent "parts by weight" and "% by weight", respectively. The softening point and melt viscosity are measured by the following method.

． Softening point: Measured by the method according to Japanese Industrial Standards (JIS) K-7234

． Melt viscosity: measured by ICI melt viscosity (150℃) cone plate method, unit is Pa．s.

． Gel Permeation Chromatography (GPC) Analysis

Manufacturer: Waters

Column: SHODEX GPC KF-601 (two), KF-602, KF-602.5, KF-603

Flow rate: 0.5ml/min.

Column temperature: 40℃

Solvent used: tetrahydrofuran (THF)

Detector: RI (differential refractometer)

．High performance liquid chromatography (HPLC) analysis

Column: Inertsil ODS-2

Flow rate: 1.0ml/min.

Column temperature: 40℃

Solvent used: acetonitrile/water

Detector: Photodiode array (225nm)

． Differential scanning calorimetry (DSC) analysis

Manufacturer: TA Instrument

Device:DSC2500

Heating rate: 10℃/min

Measuring temperature range: 30℃~350℃

． Dynamic mechanical analysis (DMA)

Manufacturer: TA Instrument

Device: DMAQ800

Measurement mode: stretching

Heating rate: 2℃/min.

Measuring temperature range: 25℃~350℃

Measuring frequency: 10Hz

The temperature at which the tanδ value is maximum is set as Tg.

．Td5 analysis

Manufacturer: Seiko Instruments Co., Ltd.

Device: Thermogravimetric-differential thermal analysis (TG/DTA) 6200

Measuring temperature range: 30℃~580℃

Heating rate: 10℃/min

．Thermomechanical analysis (TMA)

Manufacturer: TA Instrument

Device: TMAQ400

Measurement mode: stretching

Heating rate: 2℃/min.

Measuring temperature range: 25℃~330℃

． Mechanical strength

Manufacturer: Shimadzu Corporation

Device: Autograph AGS-X

Stretching speed: 0.5mm/min

The test piece is clamped in such a way that its length becomes 5 cm, and tensile measurement is performed in the 180° direction at the test speed.

．Peel strength test

Manufacturer: Shimadzu Corporation

Device: Autograph AGS-X

Peel test tensile speed: 50mm/min

The rough surface of an 18μm thick electrolytic copper foil (CF-T4X-SV-18: manufactured by Futian Metal Foil Powder Industry Co., Ltd.) and the rough surface of a 35μm thick electrolytic copper foil (CF-T9B-HTE: manufactured by Futian Metal Foil Powder Industry Co., Ltd.) were used to sandwich a curable resin composition, and the test piece was hardened at 220°C for 2 hours under a pressure of 1MPa. After the obtained test piece was cut into a width of 2cm, the 18μm thick electrolytic copper foil was cut and removed in a manner that a residual width of 1cm was left. The electrolytic copper foil with a width of 1cm and a thickness of 18μm was stretched in the 90° direction at the test speed, and the peel strength was measured.

．Water absorption test

After soaking in water for 24 hours, take it out and place it in an environment of 25℃ and 30% for 24 hours, then measure the weight to calculate.

． Dielectric constant test, dielectric loss tangent test

Manufacturer: AET Co., Ltd.

Device: 10GHz cavity resonator

Using a dryer, a test piece with a width of 2.5 mm and a length of 5 cm was dried at 120°C for 2 hours and then measured. Furthermore, the test piece was immersed in water for 24 hours, taken out, and placed in an environment of 25°C and 30% for 24 hours before being measured again.

[Synthesis Example 1]

Synthesis of aromatic amine resin (A-1)

In a flask equipped with a thermometer, cooling tube, Dean-Stark azeotropic distillation trap, and a stirrer, 192 parts of aniline, 112 parts of toluene, and 100 parts of 1,3-bis(2-hydroxy-2-propyl)benzene were placed, and 215 parts of 35% hydrochloric acid were added dropwise over 10 minutes. The temperature in the system was raised to 160°C, and the reaction was carried out at this temperature for 17 hours while distilling off water and toluene. After cooling to 80°C, 124 parts of toluene were added, and 30 parts of a 30% aqueous sodium hydroxide solution were added dropwise over 10 minutes. Thereafter, the mixture was stirred at this temperature for 2 hours and allowed to stand for 30 minutes. The separated lower water layer is removed, and the reaction solution is repeatedly washed with water until the washing solution becomes neutral. Then, the excess aniline and toluene are distilled from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 158 parts of the aromatic amine resin (A-1) represented by the formula (2). The amine equivalent of the aromatic amine resin (A-1) is 186.1 g/eq, and the softening point is 58.8°C. According to GPC analysis (RI), the n=1 body is 62.5 area%. The GPC diagram is shown in Figure 1.

[Synthesis Example 2]

Synthesis of maleimide resin (M-1)

Into a flask equipped with a thermometer, cooling tube, Dean Stark azeotropic distillation trap, and stirrer, 73.5 parts of maleic anhydride, 126 parts of toluene, 1.86 parts of methanesulfonic acid, and 12.6 parts of N-methyl-2-pyrrolidone were placed and heated to reflux. Then, while maintaining the reflux, a resin solution prepared by dissolving 93 parts of aromatic amine resin (A-1) in 55.8 parts of toluene was added dropwise over 4 hours. During this period, the condensed water and toluene azeotropically distilled under reflux conditions were cooled/separated in the Dean Stark azeotropic distillation trap, and the toluene as the organic layer was returned to the system, and the water was discharged to the outside of the system. After the resin solution was added dropwise, the reflux state was maintained and the reaction was carried out for 10 hours while dehydration was performed.

After the reaction, water washing was repeated 4 times to remove methanesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropy of toluene and water under heating and reduced pressure below 70°C. Subsequently, 2 parts of methanesulfonic acid were added, and the reaction was carried out for 4 hours under heating and reflux. After the reaction was completed, water washing was repeated 3 times until the washing water became neutral, and then water was removed from the system by azeotropy of toluene and water under heating and reduced pressure below 70°C. The solvent was removed by distillation under heating and reduced pressure until the toluene reached a resin concentration of about 70%-80%, and then additional toluene was added to adjust the resin concentration to 60%. Thus, a maleimide solution (V-1) containing the maleimide (M-1) of the present invention is obtained. According to GPC analysis (RI), the obtained maleimide resin (M-1) has an n=1 body of 57.4 area%, an n=2 body of 21.3 area%, and an n=3 body or more of 21.3 area%. According to HPLC analysis (225nm), the orientation ratio in the n=1 body (ortho-ortho body/para-para body/ortho-para body) is 32.0%/25.4%/42.6%. In addition, the softening point is 115.5°C and the viscosity is 6.0Pa. s. The GPC diagram is shown in Figure 2.

[Example 1 to Example 5, Comparative Example 1 to Comparative Example 6]

The maleimide compound and the polyphenylene ether compound having an unsaturated double bond were weighed in the ratio shown in Table 1, toluene was added to make the resin solid content 50%, and then heated and mixed at 70°C for 1 hour to prepare a varnish. The solubility and compatibility of the resin at this time were visually confirmed and evaluated under the conditions described below. The results are shown in Table 1.

Furthermore, dicumyl peroxide (DCP (dicumyl peroxide), manufactured by Nouryon Chemicals) was dissolved in the varnish as a curing accelerator. The varnish in which the curing accelerator was dissolved was heated at 80°C for 30 minutes and at 120°C for 1 hour using a vacuum dryer to prepare a curable resin composition. The obtained curable resin composition was sandwiched between copper foils, and a pressure of 1 MPa was applied under vacuum, and cured at 220°C for 2 hours. The curability at this time was confirmed and evaluated using the conditions described below. The results of various measurements of the obtained cured product are shown in Table 1.

Solubility determination criteria: ○. . . No precipitation in the solution

×．．． There is precipitation in the solution

Compatibility determination criteria: ○． ． ． Compatible

×．．． Incompatible (phase separation)

220℃ hardening judgment conditions: ○. . . Hardened material can be obtained

×．．．No hardened material was obtained (the hardened material was brittle and could not be removed)

． M-1 (obtained by removing the solvent from the product obtained in Synthesis Example 2 by distillation under heating and reduced pressure)

． MIR-3000 (made by distilling and removing the solvent from MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd.) by heating and reducing pressure)

．BMI-70 (manufactured by KI Chemical Co., Ltd.)

．BMI-2300 (manufactured by Yamato Chemical Co., Ltd.)

．SA-9000-111 (manufactured by Saudi Basic Industries Corporation (Sabic)) Mw: 3653, Mn: 2648

．OPE-2st1200 (Made by Mitsubishi Gas Chemical Co., Ltd.) Mn: 1200

In Examples 1 to 5, it was confirmed that the solvent solubility and compatibility were good, the curing reaction was carried out well at 220°C for 2 hours, and the heat resistance, copper foil peeling strength, moisture resistance, and dielectric properties were excellent. Since a large amount of maleimide compound (M-1) was used in Comparative Example 1, it was confirmed that the water absorption rate and dielectric properties were high (poor). In the case of using the maleimide compound (M-1) alone as in Comparative Example 2, it was confirmed that the heat resistance and dielectric loss tangent were good, but since the copper foil peeling strength was low and the water absorption rate was high, the dielectric loss tangent after water absorption was also deteriorated. When a polyphenylene ether compound having an unsaturated double bond is used alone as in Comparative Example 3, it does not cure under the curing conditions of 220°C and 2 hours. When other maleimide resins are used as in Comparative Examples 4 to 6, the solvent solubility or compatibility is poor, and the dielectric properties and dielectric properties after water absorption are high (poor).

Claims (4)

A curable resin composition comprises a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond, wherein the amount of the component (B) is 0.50 equivalent to 4.2 equivalents per 1 equivalent of the component (A), and the component (B) is a compound represented by the following formula (2) or a compound represented by the following formula (4).

In formula (1), R represents a hydrogen atom or a methyl group; m represents an integer from 0 to 3; n is a repeating number, the average value of which is 1<n<5.

In formula (2), n is the number of repetitions, and its average value is 1<n<10;

In formula (4), n is the number of repetitions, and its average value is 1<n<10. The hardening resin composition as described in claim 1 further contains a hardening accelerator. A prepreg, wherein the curable resin composition as described in claim 1 or 2 is retained in a sheet-shaped fiber substrate. A cured product obtained by curing the curable resin composition according to claim 1 or 2, or the prepreg according to claim 3.