TW202233718A - Curable resin composition, prepreg, and cured product of same - Google Patents

Abstract

The present invention provides: a curable resin composition having excellent heat resistance, copper foil peel strength, dielectric properties and moisture resistance; and a cured product of the curable resin composition. Provided is a curable resin composition comprising a maleimide compound (A) represented by formula (1) and a polyphenyleneether compound (B) having an unsaturated double bond, in which the ratio of the weight of the component (A) to the weight of 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 of 0 to 3, and n represents the number of repetitions in which the average value of n satisfies the formula: 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 electrical/electronic parts such as semiconductor sealing materials, printed wiring boards, build-up laminates, carbon fiber reinforced plastics, glass fiber Lightweight and high-strength materials such as reinforced plastics, and three-dimensional (3D) printing applications.

In recent years, due to the expansion of the field of use of the laminated board on which electric/electronic components are mounted, a wide range of properties and heightened requirements are required. For example, conventionally, semiconductor chips are mainly mounted on metal lead frames, but semiconductor chips with high processing capabilities such as central processing units (CPUs) are often mounted on laminates made of polymer materials. With the development of high-speed components such as CPUs and the increase in clock frequency, signal propagation delay and transmission loss have become problems, and wiring boards are required to have a low dielectric constant or a low dielectric loss tangent.

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

In addition, in recent years, due to the popularization of mobile electronic devices such as mobile phones, precision electronic devices have been carried to outdoor environments or used in close proximity to the human body. Therefore, resistance to external environments (especially heat-and-moisture environments) is required. Furthermore, in the field of automobiles, with the rapid development of electronics, precision electronic devices are sometimes placed near the engine, and higher levels of heat and humidity resistance are required.

Wiring boards using BT resin, which is a resin that uses a bisphenol A-type cyanate ester compound and a bismaleimide compound in combination as in Patent Document 1, are excellent in heat resistance, chemical resistance, dielectric properties, and the like. It is widely used as a high-performance wiring board, but needs to be improved in order to cope with further high performance as described above.

In this case, the commercially available maleimide resins have significantly improved heat resistance compared to epoxy resins conventionally used in the above-mentioned applications, and exhibit excellent dielectric properties in the high-frequency region. However, the maleimide resin having high heat resistance has the following disadvantages: low moisture resistance, brittleness due to rigidity, and low adhesion to copper foil.

On the other hand, maleimide resins such as Patent Document 2 and Patent Document 3 have also been developed, but they are not sufficient.

In addition, a composition comprising a maleimide resin and a propylene group-containing phenol resin as in Patent Document 4 has been proposed, but the phenolic hydroxyl group that does not participate in the reaction at the time of curing reaction remains, so the dielectric properties are not sufficient. In addition, 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 Laid-Open No. 3-100016 [Patent Document 3] Japanese Patent No. 5030297 [Patent Document 4] Japanese Patent Laid-Open No. 04-359911 [Patent Document 5] Japanese Patent Laid-Open No. 4-75222 [Patent Document 6] Japanese Patent Laid-Open No. 6-37465

[The problem to be solved by the invention] The present invention was made in view of such a situation, and an object thereof is to provide a curable resin composition and a cured product thereof exhibiting excellent heat resistance, copper foil peel strength, dielectric properties, and moisture resistance. [Means of Solving Problems]

The inventors of the present invention have made diligent studies to solve the above-mentioned problems, and as a result, found that the heat resistance of a cured product of a curable resin composition comprising a maleimide compound having a specific structure and a polyphenylene ether compound having an unsaturated double bond , copper foil peeling strength, dielectric properties, and moisture resistance are excellent, thereby completing the present invention.

That is, the present invention relates to the following [1] to [7]. [1] A curable resin composition comprising a maleimide compound (A) represented by the following formula (1), a polyphenylene ether compound (B) having an unsaturated double bond, a component (A) and a component (B) ) in a weight ratio of 50/50 to 5/95.

[hua 1]

(In formula (1), R represents a hydrogen atom or a methyl group. m represents an integer of 0 to 3. n is a repeating number, and the average value is 1<n<5.) [2] A curable resin composition containing a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond in an amount of 1 equivalent relative to the component (A) , the component (B) is 0.20 to 4.2 equivalents.

[hua 2]

(In formula (1), R represents a hydrogen atom or a methyl group. m represents an integer of 0 to 3. n is a repeating number, and the average value is 1<n<5.) [3] The curable resin composition according to 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 according to 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) compound of.

[hua 3]

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

[hua 4]

(In formula (4), n is the number of repetitions, and the average value thereof is 1<n<10.) [5] The curable resin composition according to any one of [1] to [4] above, which further contains a curing accelerator. [6] A prepreg obtained by holding the curable resin composition according to any one of the above items [1] to [5] in a sheet-like fiber base material. [7] A cured product obtained by curing the curable resin composition according to any one of the above [1] to [5], or the prepreg according to the above [6]. [Effect of invention]

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

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

[hua 5]

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

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

[hua 6]

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

In the above formula (1), when n=1, the solubility in the solvent is low, and when n is 5 or more, the fluidity at the time of molding is deteriorated, and the cured product cannot be sufficiently exhibited. characteristic.

The component (A) preferably has a molecular weight distribution, and in the formula (1), the content obtained by GPC analysis (RI) of n=1 body is preferably 98 area % or less, more preferably 20 area % to 90 area %, more preferably 30 area % to 80 area %, particularly preferably 40 area % to 80 area %. Heat resistance becomes favorable as content of n=1 body is 98 area % or less. In addition, the crystallinity decreased, and the solvent solubility became favorable. On the other hand, when the lower limit value of n=1 body is 20 area % or more, the viscosity of the resin solution decreases, and the impregnation property becomes favorable. In addition, since the solvent can be removed at low temperature when taken out as a solid, self-polymerization does not easily occur, and the handling becomes easy.

Component (A) increases the proportion of asymmetric structures having different orientations with respect to maleimide groups, so that solvent solubility becomes favorable, and dielectric properties can be improved in the cured product. The alignment ratio in the n=1 body of the formula (1) can be obtained according to high performance liquid chromatography (high performance liquid chromatography, HPLC) analysis (225 nm), and the ortho-para body is preferably n = 30 area % or more and less than 60 area % in the total body amount, more preferably 35 area % or more and less than 55 area %, particularly preferably 40 area % or more and less than 55 area %.

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

Hereinafter, although the manufacturing method of a component (A) is demonstrated, it is not limited to this manufacturing method.

[Manufacturing method of aromatic amine resin] As the component (A), an aromatic amine resin represented by the following formula (3) can be used as a precursor.

[hua 7]

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

The method for producing the aromatic amine resin represented by the formula (3) is not particularly limited. Benzene is reacted at 180°C to 250°C in the presence of an acidic catalyst to obtain the n=1 body in the formula (3) as a main component. In the body of n=1, it contains a symmetrical structure with the same alignment with respect to 2 molecules of aniline, such as 1,3-bis(p-aminocumyl)benzene and 1,3-bis(o-aminocumyl)benzene The compound; such as 1-(o-aminocumyl)-3-(p-aminocumyl)benzene, three isomers of asymmetric structure compounds with different orientations relative to aniline 2 molecules. Furthermore, n=2 to 5 forms are also produced as subcomponents, but in Patent Document 5, these are purified by crystallization to obtain 1,3-bis(p-aminocumyl)benzene with a purity of 98% . In addition, in Patent Document 6, 1,3-bis(p-aminocumyl)benzene is maleimidized to synthesize N,N'-(1,3-phenylene-bis-(2, 2-Propylidene)-bis-p-phenylene)bismaleimide, obtained as a crystalline product, but it needs to be heated in order to dissolve it in a solvent, and if it is placed at room temperature after heating , it crystallizes out within a few hours. Therefore, there is a possibility of precipitation of crystals even when the resin composition is adjusted. N,N'-(1,3-phenylene-bis-(2,2-propylene)-bis-paratylene The higher the concentration of phenyl)bismaleimide, the higher the likelihood of crystallization. In order to produce printed wiring boards or composite materials, glass cloth or carbon fiber is impregnated in varnish to adhere resin. However, if crystals are precipitated, impregnation cannot be performed. On the other hand, if the temperature is increased to maintain the dissolved state, the composition will The reaction of the varnish will be accelerated and the working time of the varnish will be shortened.

When synthesizing the aromatic amine resin represented by the above formula (3), the acidic catalyst to be used includes hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, Acid catalysts such as methanesulfonic acid, etc. In the present invention, protic 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. With respect to 100% by weight of the aniline used, the amount of catalyst used is preferably 1% by weight to 12% by weight, more preferably 1% by weight to 10% by weight, and particularly preferably 1% by weight to 7% by weight. If it exceeds 12 weight %, the target asymmetric structure compound will be few, and the compound which has a symmetrical structure will be formed preferentially. On the other hand, if it is less than 1%, not only the progress of the reaction becomes slow, but also the reaction may not be completed, so it is not preferable.

The reaction may be performed using organic solvents such as toluene and xylene as necessary, or may be performed without a solvent. For example, when an acidic catalyst is added to a mixed solution of aniline and a solvent, and the catalyst contains water, it is preferable to remove water from the system by azeotropy. Then, diisopropenylbenzene or bis(α-hydroxyisopropyl)benzene is added, and the temperature is raised while removing the solvent from the system, and the temperature is raised at 140°C to 190°C, preferably 160°C to 190°C for 5 hours to 50°C. hours, preferably 5 to 30 hours. When the reaction temperature is too high, rebonding occurs after the asymmetric structure is formed, and the symmetric structure is preferentially formed, so that the intended solvent solubility and electrical properties cannot be exhibited. When bis(α-hydroxyisopropyl)benzene is used, water is by-produced, so it is removed from the system while azeotroping with the solvent when the temperature is raised. After the reaction was completed, the acidic catalyst was neutralized with an aqueous alkaline solution, and a water-insoluble organic solvent was added to the oil layer, and the water was repeatedly washed until the wastewater became neutral, and then the solvent and excess aniline derivatives were removed under heating and reduced pressure. In the case of using activated clay or ion exchange resin, after the reaction is completed, the reaction solution is filtered to remove the catalyst. In addition, since diphenylamine is by-produced depending on the reaction temperature and the type of catalyst, it is preferable to remove it as necessary. The diphenylamine derivative is removed to 1 wt % or less, preferably 0.5 wt % or less, and more preferably 0.2 wt % or less, under high temperature/high vacuum, or by means of steam distillation or the like.

[Manufacturing method of maleimide resin] Component (A) can be obtained by mixing the aromatic amine resin represented by the formula (3) obtained by the above steps, with maleic acid or maleic anhydride (hereinafter, also referred to as "maleic acid"). Acid anhydrous ".) in the presence of a solvent and a catalyst for addition or dehydration condensation reaction.

The solvent used in the reaction needs to remove the water generated in the reaction from the system, so it is preferable to use a water-insoluble solvent. For example, 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-based solvents such as butyl ketone and cyclopentanone, etc. are not limited to these, and two or more of them may be used in combination.

Moreover, in addition to the said water-insoluble solvent, an aprotic polar solvent may be used together. For example, dimethylsulfoxide, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and N-methyl-2-pyrrole can be mentioned. A pyridone or the like may be used in combination of two or more. In the case of using an aprotic polar solvent, it is preferable to use one having a higher boiling point than the water-insoluble 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, and the like. The usage-amount of an acid catalyst is 0.1 to 10 weight% normally with respect to an aromatic amine resin, Preferably it is 1 to 5 weight%.

For example, the aromatic amine resin represented by the formula (3) is dissolved in toluene and N-methyl-2-pyrrolidone, and anhydrous maleic acid is added thereto to generate amide acid, and then p-toluene is added. The sulfonic acid reacts while removing water produced under reflux conditions from the system.

Alternatively, anhydrous maleic acid is dissolved in toluene, and the N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the formula (3) is added with stirring to generate amide acid, followed by adding The p-toluenesulfonic acid was reacted while removing water generated under reflux conditions from the system.

Alternatively, the N-methyl-2-pyrrole of the aromatic amine resin represented by the above formula (3) is added dropwise under stirring/reflux while dissolving anhydrous maleic acid in toluene and adding p-toluenesulfonic acid. The pyridone solution was subjected to the reaction while removing the water produced during azeotropy to the outside of the system and returning toluene to the system (the above is the first-stage reaction).

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

In order to reduce the unclosed amide acid, water is added to the reaction solution after the maleimidization reaction listed above, so that it is separated into a resin solution layer and a water layer, due to excess maleic acid or maleic acid. Acid anhydrides, aprotic polar solvents, catalysts, etc. are dissolved in the water layer, so they are separated and removed, and the same operation is repeated repeatedly to remove excess maleic acid or maleic anhydride, aprotic polar solvents, and catalysts. Remove completely. The catalyst is added to the maleimide resin solution from which excess maleic acid or maleic anhydride, aprotic polar solvent, and the organic layer of the catalyst have been removed, and the residual amide acid is heated and refluxed again. The dehydration and ring-closure reaction of the above method can obtain the maleimide resin solution with low acid value (the above is the second-stage reaction).

The time for the re-dehydration and ring-closure reaction is usually 1 hour to 5 hours, preferably 1 hour to 3 hours, and the aprotic polar solvent may also be added if necessary. After the reaction was completed, it was cooled and washed with water repeatedly until the washing water became neutral. Then, after removing water by azeotropic dehydration under heating and reducing pressure, the solvent may be distilled off, or another solvent may be added to adjust the resin solution to a desired concentration, or the solvent may be completely distilled off and taken out as a solid resin.

Next, the component (B) will be described. The component (B) is not particularly limited as long as it has an unsaturated double bond and a polyphenylene ether structure. Examples of the unsaturated double bond in the component (B) include (meth)acrylic group, styryl group, allyl group, vinyl group, and methallyl group, preferably (meth)acrylic acid group. base. As a commercial item, SA-9000-111 represented by the following formula (2) (a polyphenylene ether compound having a methacrylic acid group, manufactured by Saudi Basic Industries Corporation (Sabic)) or the following OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., polyphenylene ether compound having a styrene group) represented by the above formula (4), etc. In particular, a compound represented by the following formula (2) is preferred from the viewpoint of dielectric properties.

[hua 8]

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

[Chemical 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 the component (B) is preferably 500 to 5000, more preferably 2000 to 5000, and still more preferably 2000 to 4000. When the molecular weight is 500 or more, the heat resistance of the cured product is improved. When the molecular weight is 5000 or less, the melt viscosity decreases, sufficient fluidity is obtained, and the moldability is good. In addition, since the reactivity is improved, 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 or the like.

Component (B) can be imparted with radical polymerizability by reacting a polyphenylene ether compound with a compound having an unsaturated double bond, such as methacryloyl chloride, acryl chloride, and chloromethylstyrene.

The polyphenylene ether compound can be obtained by a polymerization reaction, or can be obtained by subjecting a high molecular weight polyphenylene ether compound having a weight average molecular weight of 10,000 to 30,000 to a redistribution reaction. In the redistribution reaction, for example, a high molecular weight polyphenylene ether compound is heated in a solvent such as toluene in the presence of a phenol compound and a radical initiator to perform a redistribution reaction. Since the polyphenylene ether compound obtained by the redistribution reaction in this way has hydroxyl groups derived from the phenolic compound that contribute to hardening at both ends of the molecular chain, higher heat resistance can be maintained, and in this respect, it is relatively high. good. In addition, a polyphenylene ether compound obtained by a polymerization reaction is preferable in that it exhibits excellent fluidity.

In the case of a polyphenylene ether compound obtained by a polymerization reaction, adjustment of the molecular weight of the polyphenylene ether compound can be performed by adjusting polymerization conditions and the like. In addition, in the case of the polyphenylene ether compound obtained by the redistribution reaction, the molecular weight can be adjusted by adjusting the conditions of the redistribution reaction and the like. More specifically, adjustment of the compounding amount of the phenolic compound used for the redistribution reaction, etc. can be considered. That is, the molecular weight of the component polyphenylene ether compound obtained is low, so that the compounding quantity of a phenol type compound is large.

Moreover, as a polyphenylene ether compound, poly (2, 6- dimethyl- 1, 4- phenylene ether) etc. are mentioned specifically, for example. That is, in the case of the component (B) obtained by the redistribution reaction, poly(2,6-dimethyl-1,4-phenylene ether) can be used as the high molecular weight polyphenylene ether compound. The obtained polyphenylene ether compounds, etc. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, for example, compounds having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolak, cresol novolak, etc., can be preferably used. Multifunctional phenolic compounds. These may be used alone or in combination of two or more.

The weight ratio of the component (A) to the 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, still more preferably 25/ 75～5/95, especially 25/75～10/90. In addition, as the functional group equivalent ratio of the component (A) to the component (B), the component (B) is preferably 0.2 to 4.2 equivalents, more preferably 0.5 to 4.2 equivalents, relative to 1 equivalent of the component (A), and further It is preferably 0.7 equivalents to 4.2 equivalents, and particularly preferably 0.7 equivalents to 2.0 equivalents. When the component (B) is less than 0.2 equivalents, since the maleimide group increases, the water absorption property deteriorates, and the cured product becomes brittle, so that the copper foil peeling strength 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, any known resin materials may be used other than the component (A) and the component (B). Specifically, phenol resins, epoxy resins, amine resins, reactive olefin-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate resins, acryl-based resins, methallyl resins can be mentioned. A base resin, an active ester resin, etc., may use 1 type, and may use multiple types together. Moreover, you may use together the maleimide compound other than a component (A).

As phenol resins, epoxy resins, amine resins, reactive olefin-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, and active ester resins, the resins exemplified below can be used, respectively. It is not limited to these.

Phenol resins: Phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxy Naphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde (cinnamaldehyde), polycondensates of furfural, etc.); phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene , divinyl biphenyl, diisopropenyl biphenyl, butadiene, isoprene, etc.) polymers; phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene Polycondensates of ethyl ketone, benzophenone, etc.); by 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.) polycondensation obtained phenol resin; bisphenols and various aldehyde polycondensates; polyphenylene ether.

Epoxy resin: the phenol resin; glycidyl ether epoxy resin obtained by glycidylation of alcohols, etc.; 4-vinyl-1-cyclohexene diepoxide or 3,4-cyclohexene Alicyclic epoxy resins represented by oxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, etc.; tetraglycidyl diamino diphenylmethane (TGDDM) or Glycidylamine-based epoxy resins represented by triglycidyl-p-aminophenol, etc.; glycidyl ester-based epoxy resins.

Amine resins: diaminodiphenylmethane; diaminodiphenyl ash; isophorone diamine; naphthalene diamine; aniline novolac; o-ethylaniline novolac; Aniline resin obtained by the reaction of xylylene chloride; aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(chloromethyl)-1,1'-biphenyl and 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(methoxy) Amine resin obtained by the reaction of methyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.).

Resin containing active olefin: polycondensation of the phenol resin and halogen-based compound containing active olefin (chloromethylstyrene, allyl chloride, methylallyl chloride, acryl chloride, etc.) compounds; 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, Polycondensates of 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.; epoxy resins or alcohols with substituted or unsubstituted Polycondensates of substituted acrylates (acrylates, methacrylates, etc.); maleimide resins (4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, etc.) Amine, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5, 5'-Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl Ether bismaleimide, 4,4'-diphenyl bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4 -maleimidephenoxy)benzene).

Isocyanate resins: p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane Aromatic diisocyanates such as diisocyanate and naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate Diisocyanates of aliphatic or alicyclic structure such as isocyanates and lysine diisocyanates; polyisocyanates such as isocyanate bodies such as one or more biuret bodies of isocyanate monomers or trimerization of the diisocyanate compounds; A polyisocyanate obtained by urethane reaction of the isocyanate compound and a polyol compound.

Polyamide resin: selected from amino acids (6-aminohexanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, p-aminomethylbenzoic acid, etc.), lactamide (ε-caprolactam, ω-undecanalactamide, ω-lauryl amide) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine Amines, Hexamethylenediamine, Heptamethylenediamine, Octamethylenediamine, Nonamethylenediamine, Decanediamine, Undecanediamine, Dodecanediamine, Tridecanediamine Amine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1 ,5-diaminopentane, 2-methyl-1,8-diaminooctane and other aliphatic diamines; cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3 - Alicyclic diamines such as methyl-4-aminocyclohexyl) methane; aromatic diamines such as xylene diamine, etc.) and dicarboxylic acids (oxalic acid, malonic acid, succinic acid, glutaric acid, hexane Aliphatic dicarboxylic acids such as diacid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid , 2-methyl terephthalic acid, 5-methyl isophthalic acid, isophthalic acid-5-sodium sulfonate, hexahydroterephthalic acid, hexahydroisophthalic acid and other aromatic dicarboxylic acids; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters and dichlorides of these dicarboxylic acids) are the main raw materials of the polymer.

Polyimide resin: the diamine and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 5-(2,5-dioxotetrahydro- 3-furyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-mellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic Acid dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4 '-Diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2'-propylene-4,4'-diphthalic acid Dianhydride, 1,2-ethylidene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetra Methylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic acid Formic acid dianhydride, thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxybenzene base) phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3- Bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride 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]propanedianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanedianhydride, bis( 3,4-Dicarboxyphenoxy) dimethylsiloxane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride , 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 3,4, 9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-Anthracene tetracarboxylic dianhydride, 1,2,7,8-Phenanthrene tetracarboxylic dianhydride, Ethylene tetracarboxylic dianhydride, 1, 2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3, 4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4' -Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylidene base-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 dianhydride, rel-[1S,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 acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride) ), 9,9'-bis(3,4-dicarboxyphenyl) fluorene dianhydride) polycondensate.

Cyanate resin: It is a cyanate compound obtained by reacting a phenol resin with a cyanogen halide. Specific examples include dicyanatobenzene, tricyanobenzene, and dicyanonaphthalene. , dicyanooxybiphenyl, 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyano) oxyphenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanooxyphenyl)propane, 2,2'-bis(4-cyanooxyphenyl)ethane, 2,2'-bis(4-cyanooxyphenyl)hexafluoropropane, bis(4-cyanoxyphenyl)sulfane, bis(4-cyanoxyphenyl)sulfide, phenol novolac cyanate , a phenol-dicyclopentadiene co-condensate converted from a hydroxyl group to a cyanate group, etc., but not limited to these. In addition, the cyanate ester compound of which the synthesis method is described in Japanese Patent Laid-Open No. 2005-264154 is particularly preferred as a cyanate ester compound because it is excellent in low moisture absorption, flame retardancy, and dielectric properties. The cyanate resin may contain zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, Zinc octoate, tin octoate, lead acetylacetonate, dibutyltin maleate and other catalysts. The catalyst is usually used in 0.0001 to 0.10 parts by mass, preferably 0.00015 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 curing agent for curable resins such as epoxy resins as needed. As the active ester-based hardener, phenolic esters, thiophenolic esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are preferably those having two or more highly reactive ester groups in one molecule. compound. The active ester-based curing agent is preferably obtained by a condensation reaction of at least any one of a carboxylic acid compound and a thiocarboxylic acid compound, and at least one of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferred, and it is preferably obtained from at least one of a carboxylic acid compound, a phenol compound, and a naphthol compound. active ester hardener. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methyl 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, phloroglucin, dicyclopentane Diene-type diphenol compounds, phenol novolacs, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol in one molecule of dicyclopentadiene. Preferable specific examples of the active ester-based curing agent include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, and active esters containing an acetylated compound of phenol novolac. Compounds, active ester compounds comprising benzyl compounds of phenol novolacs. Among them, the active ester compound containing a naphthalene structure and the active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit including phenylene-dicyclopentylene-phenylene. Examples of commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" which are active ester compounds containing a dicyclopentadiene-type diphenol structure. , "HPC-8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC); "EXB9416-70BK" (DIC) as an active ester compound containing a naphthalene structure DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a phenol novolak acetylated compound; "DC808" as an active ester compound containing a phenol novolak benzyl compound YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation), which is an active ester-based hardener that is an acetylated compound of phenol novolak; "EXB-9050L-62M" manufactured by DIC, an ester-based hardener, etc.

The curable resin composition of the present invention may further use a curing accelerator (curing catalyst) in combination to improve curability. As a specific example of a hardening accelerator that can be used, it is preferable to use free radicals for the purpose of promoting self-polymerization of radically polymerizable curable resins such as olefin resins and maleimide resins or radical polymerization with other components. base polymerization initiator. Examples of the radical polymerization initiator include: ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; diacyl peroxides such as benzyl peroxide; dicumyl peroxide compounds, 1,3-bis(tert-butylperoxyisopropyl)benzene and other dialkyl peroxides; tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy ring Peroxy ketals such as hexane; α-cumyl peroxy neodecanoate, tert-butyl peroxy neodecanoate, tert-butyl peroxytrimethyl acetate, 1,1,3, 3-Tetramethylbutylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tertiary Amyl peroxy-3,5,5-trimethylhexanoate, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-amyl peroxybenzoate, etc. Peroxyesters; di-2-ethylhexyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butylperoxyisopropylcarbonate, 1 ,6-bis(tert-butyl peroxycarbonyloxy) hexane and other peroxycarbonates; tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxycaprylate, peroxide Laureth and other organic peroxides or azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile) ) and other well-known hardening accelerators of azo-based compounds, but are not particularly limited to these. Preferred are ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peroxyesters, peroxycarbonates ( peroxycarbonate) and the like, more preferably dialkyl peroxides. As an addition amount of a radical polymerization initiator, 0.01-5 mass parts is preferable with respect to 100 mass parts of curable resin compositions, and 0.01-3 mass parts is especially preferable. When the amount of the radical polymerization initiator used is large, the dielectric properties of the cured product are deteriorated.

The curable resin composition of the present invention may be added or used in combination with curing accelerators other than the radical polymerization initiator as necessary. Specific examples of the curing accelerator that can be used include tris such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo(5,4,0)undecene-7 Grade amines; phosphines such as triphenylphosphine; tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethylammonium salt Quaternary ammonium salts such as ammonium hydroxide; Hydroxide ions and the like are not particularly specified, but organic acid ions and hydroxide ions are particularly preferred.), tin octoate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, Transition metal compounds (transition metal salts) such as zinc compounds (zinc myristate) or zinc phosphate (zinc octyl phosphate, zinc stearyl phosphate, etc.), etc. About the compounding quantity of a hardening accelerator, 0.01 weight part - 5.0 weight part can be used as needed with respect to 100 weight part of curable resin compositions.

Furthermore, the curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy imparting component. The phosphorus-containing compound may be either a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, tolyldiphenyl phosphate, tolyl-2 , 6-bis(xylyl) phosphate, 1,3-phenylene bis(bis(xylyl) phosphate), 1,4-phenylene bis(bis(xylyl) phosphate), Phosphate esters such as 4,4'-biphenyl (bis(xylyl) phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2 ,5-dihydroxyphenyl)-10H-9-oxa-10-phosphane-10-oxide and other phosphanes; obtained by reacting epoxy resin with the active hydrogen of the phosphanes Phosphorus-containing epoxy compounds, red phosphorus, etc., are preferably phosphoric acid esters, phosphoranes or phosphorus-containing epoxy compounds, especially 1,3-phenylene bis(bis(xylyl) phosphate), 1,4-phenylene bis(bis(xylyl) phosphate), 4,4'-biphenyl(bis(xylyl) phosphate) or phosphorus-containing epoxy compounds. The content of the phosphorus-containing compound is preferably in the range of (phosphorus-containing compound)/resin component in the curable resin composition from 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy will be insufficient, and if it is 0.6 or more, the hygroscopicity and dielectric properties of the cured product may be adversely affected.

Furthermore, a light stabilizer may be added to the curable resin composition of this invention as needed. The light stabilizer is preferably a hindered amine light stabilizer, and particularly preferably a hindered amine light stabilizer (Hindered Amine Light Stabilizer, HALS). The HALS is not particularly limited, but typical examples include 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 polycondensate, dimethyl succinate- 1-(2-Hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, 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) yl-4-piperidinyl)sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2, 6,6-pentamethyl-4-piperidinyl) ester and the like. Only one type of HALS may be used, or two or more types may be used in combination.

Furthermore, in the curable resin composition of this invention, a binder resin can also be mix|blended as needed. Examples of the binder resin include butyral-based resins, acetal-based resins, acrylic-based resins, epoxy-nylon-based resins, nitrile butadiene rubber (NBR)-phenol-based resins, epoxy- NBR-based resins, polyimide-based resins, polyimide-based resins, silicone-based resins, etc. are not limited to these. The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 parts by mass relative to 100 parts by mass of the resin component ~20 parts by mass.

Furthermore, fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, carbide can be added to the curable resin composition of the present invention as needed Silicon, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc (talc), clay, iron oxide, asbestos (asbestos), glass powder and other powders, or inorganic fillers made of spherical or crushed materials. In addition, in the case of obtaining a curable resin composition for semiconductor encapsulation in particular, the amount of the inorganic filler used in the curable resin composition is usually 80 to 92 mass %, preferably 83 mass % % to 90% by mass.

Furthermore, a well-known additive can be mix|blended with the curable resin composition of this invention as needed. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, and silicone gel. Surface treatment agent, mold release agent, carbon black, phthalocyanine blue, phthalocyanine green and other colorants for fillers such as glue, silicone oil, and silane coupling agent. The blending amount of these additives is preferably 1,000 parts by mass or less, 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 predetermined ratio, and is usually pre-cured at 130° C. to 180° C. for 30 seconds to 500 seconds, and further at 150° C. to 200° C. By post-curing at ℃ for 2 hours to 15 hours, a sufficient curing reaction proceeds, and the cured product of the present invention is obtained. In addition, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and the solvent may be removed and then cured.

The curable resin composition of the present invention obtained in this way has moisture resistance, heat resistance, high adhesiveness, low dielectric constant, and low dielectric loss tangent. Therefore, the curable resin composition of the present invention can be used in a wide range of fields requiring moisture resistance, heat resistance, high adhesiveness, low dielectric constant, and low dielectric loss tangent. Specifically, it can be effectively used as insulating materials, laminates (printed wiring boards, substrates for ball grid array (BGA), build-up substrates, etc.), sealing materials, and resists for all electrical/electronic parts. Material. In addition to forming materials and composite materials, it can also be used in the fields of coating materials, adhesives, and 3D printing. 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 semiconductor devices include dual in-line packages (DIPs), quad flat packages (QFPs), ball grid arrays (BGAs), die-scale packages ( 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 can be prepared by dispersing or dissolving each component in a solvent or the like, mixing uniformly, and distilling off the solvent if necessary, or by dispersing or dissolving the components in a solvent as described above. Prepolymerization is possible. For example, prepolymerization is performed by heating the component (A) and the component (B) in the presence or absence of a catalyst and 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 ester compounds, phenol resins, acid anhydride compounds, and other additives may be added. Prepolymerization is carried out. For mixing or prepolymerization of each component, for example, an extruder, a kneader, a roll, etc. are used in the absence of a solvent, and a reactor with a stirring device or the like is used in the presence of a solvent.

As a method of mixing uniformly without using a solvent or the like, mixing is performed at a temperature in the range of 50°C to 100°C using a device such as a kneader, a roller, a planetary mixer, etc., so as to be uniformly mixed. curable resin composition. The obtained curable resin composition can also be pulverized and then molded into a cylindrical ingot by a molding machine such as a tablet machine, or into a granular powder or a powder molded body, or a mixture of these. The composition is melted on the surface support, and molded into a sheet shape having a thickness of 0.05 mm to 10 mm, thereby obtaining a curable resin composition molded body. The obtained molded body was a non-tacky molded body at 0°C to 20°C, and even when stored at -25°C to 0°C for 1 week or more, the fluidity and curability hardly decreased. The obtained molded body can be molded into a cured product using a transfer injection molding machine or a compression molding machine.

An organic solvent may be added to the curable resin composition of this invention, and it may be set as a varnish-like composition (henceforth, it is also abbreviated as a varnish.). If necessary, the curable resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methyl acetone It is made into varnish in a solvent such as pyrrolidone, impregnated in glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other substrates, heated and dried, and the obtained prepreg is hot pressed By molding, a cured product of the curable resin composition of the present invention can be obtained. The solvent in this case is usually used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the curable resin composition of the present invention and the solvent. If the amount of solvent is less than this range, the viscosity of the varnish will increase, and workability will be deteriorated, and if the amount of solvent is large, it will cause voids in the cured product. In addition, if it is a liquid composition, a curable resin cured product containing carbon fibers can be obtained directly, for example, by resin transfer molding (RTM) method.

Moreover, the curable composition of this invention can also be used as a modifier of a film-type composition. Specifically, it can be used in the case of improving the flexibility of the B-stage and the like. For the resin composition of this film type, the curable resin composition of the present invention is made into the curable resin composition varnish and coated on the release film, and after removing the solvent under heating, it is B-staged. This is obtained as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like.

The curable resin composition of the present invention can be heated, melted, and reduced in viscosity, and impregnated with 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 further include inorganic fibers other than glass. or polyparaphenylene terephthalamide (kevlar (registered trademark), manufactured by Dupont Co., Ltd.), wholly aromatic polyamide, polyester; and polyparatylene Organic fibers such as polyparaphenylene benzoxazole, polyimide, and carbon fibers are not particularly limited to these. Although it does not specifically limit as a shape of a base material, For example, a woven fabric, a nonwoven fabric, a roving (roving), a chopped strand mat (chopped strand mat) etc. are mentioned. In addition, as the weave of the woven fabric, a plain weave, a basket weave, a twill weave, etc. are known, and it can be appropriately selected and used from these known weaves according to the intended use and performance. In addition, it is preferable to use a glass woven fabric that has been subjected to a fiber opening treatment on the woven fabric, or a glass woven fabric that has been surface-treated with a silane coupling agent or the like. The thickness of the base material is not particularly limited, but is preferably about 0.01 mm to 0.4 mm. In addition, a prepreg can also be obtained by impregnating the varnish in a reinforcing fiber and heating and drying it.

The laminate of the present embodiment includes one or more pieces of the prepreg. The laminate is not particularly limited as long as it includes one or more prepregs, and may have any other layer. As a manufacturing method of a laminated board, a generally well-known method can be suitably applied, and it does not specifically limit. For example, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used in the molding of a metal foil-clad laminate, and the prepregs can be laminated and heated. Press-formed to obtain a laminate. In this case, the heating temperature is not particularly limited, but is preferably 65°C to 300°C, more preferably 120°C to 270°C. In addition, the pressure of the pressing is not particularly limited. If the pressure is too large, the solid content of the resin of the laminate will be difficult to adjust and the quality will be unstable. If the pressure is too small, the adhesion between the bubbles and the laminate will be deteriorated. Therefore, it is preferably 2.0 MPa to 5.0 MPa, more preferably 2.5 MPa to 4.0 MPa. The laminated board of this embodiment can be suitably used as a laminated board with a metal foil which is mentioned later by including the layer which has a metal foil. The prepreg is cut into a desired shape, laminated with copper foil or the like as necessary, and then press-molded, autoclave, sheet-winding, or the like is applied to the laminate. The curable resin composition is heated and hardened, whereby a laminated board (printed wiring board) for electrical and electronic use or a carbon fiber reinforced material can be obtained.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and paints. The cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, and thus can be preferably used for a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, and organic electroluminescence (electroluminescence, EL) components for sealing materials, printed wiring boards, electrical and electronic parts such as build-up laminates, or composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics. [Example]

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, "part" and "%" in this document represent "weight part" and "weight %", respectively. The softening point and melt viscosity were measured by the following methods. ･Softening point: Measured by a method based on Japanese Industrial Standards (JIS) K-7234 ･Melt viscosity: measured by the ICI melt viscosity (150℃) cone and plate method, the unit is Pa·s.

･Gel permeation chromatography (GPC) analysis Manufacturer: Waters Column: SHODEX (SHODEX) GPC KF-601 (two), KF-602, KF-602.5, KF-603 Flow rate: 0.5 ml/min. Column temperature: 40℃ Solvent used: tetrahydrofuran (tetrahydrofuran, THF) Detector: RI (Differential Refraction Detector)

･Analysis by high performance liquid chromatography (HPLC) String: Inertsil ODS-2 Flow rate: 1.0 ml/min. Column temperature: 40℃ Solvent used: acetonitrile/water Detector: Photodiode array (225 nm)

･Differential scanning calorimetry (DSC) analysis Manufacturer: TA Instrument Device: DSC2500 Heating rate: 10℃/min Measurement temperature range: 30℃～350℃

･Dynamic mechanical analysis (DMA) Manufacturer: TA Instrument Device: DMAQ800 Measurement Mode: Stretch Heating rate: 2℃/min. Measurement temperature range: 25℃～350℃ Measurement frequency: 10 Hz The temperature at which the value of tanδ is the largest is set as Tg.

･Td5 analysis Manufacturer: Seiko Instruments Co., Ltd. Device: Thermogravimetric-differential thermal analysis (TG/DTA) 6200 Measurement temperature range: 30℃～580℃ Heating rate: 10℃/min

･Thermomechanical analysis (TMA) Manufacturer: TA Instrument Device: TMAQ400 Measurement Mode: Stretch Heating rate: 2℃/min. Measurement temperature range: 25℃～330℃

·Mechanical strength Manufacturer: Shimadzu Corporation Installation: Autograph AGS-X Tensile speed: 0.5 mm/min The test piece was clamped so that the length of the test piece would be 5 cm, and the tensile measurement was performed in the 180° direction at the test speed.

･Peel strength test Manufacturer: Shimadzu Corporation Installation: Autograph AGS-X Peel test tensile speed: 50 mm/min Using the rough surface of 18 μm thick electrolytic copper foil (CF-T4X-SV-18: manufactured by Futian Metal Foil Industry Co., Ltd.) and 35 μm thick electrolytic copper foil (CF-T9B-HTE: Futian Metal Foil Powder Industry Co., Ltd. Co., Ltd.) sandwiched the curable resin composition on the rough surface, and cured it under a pressure of 1 MPa at 220° C. for 2 hours to prepare a test piece. After cutting the obtained test piece into a width of 2 cm, the electrolytic copper foil with a thickness of 18 μm was cut and removed so as to have a remaining width of 1 cm. The electrodeposited copper foil having a width of 1 cm and a thickness of 18 μm was stretched in the 90° direction at the test speed, and the peel strength was measured.

･Water absorption test After being immersed in water for 24 hours, it was taken out, left to stand for 24 hours in an environment of 25° C. and 30%, and then calculated by measuring the weight.

･Dielectric constant test, dielectric loss tangent test Manufacturer: AET Corporation Device: 10 GHz Cavity Resonator The measurement was performed after drying the test piece with a width of 2.5 mm and a length of 5 cm at 120° C. for 2 hours using a dryer. Furthermore, after immersing the test piece in water for 24 hours, it was taken out, and after being left to stand for 24 hours in an environment of 25°C and 30%, the measurement was performed again.

[Synthesis Example 1] Synthesis of Aromatic Amine Resin (A-1) 192 parts of aniline, 112 parts of toluene, 1,3-bis(2-hydroxy-2) were charged into a flask equipped with a thermometer, a cooling tube, a Dean-Stark azeotropic distillation trap, and a stirrer 100 parts of -propyl)benzene, 21.5 parts of 35% hydrochloric acid was added dropwise over 10 minutes. The temperature in the system was raised to 160°C, and the reaction was performed at this temperature for 17 hours while distilling off water and toluene. Then, after cooling to 80° C., 124 parts of toluene was added, and 30 parts of a 30% aqueous sodium hydroxide solution was added dropwise over 10 minutes. Then, it stirred at this temperature for 2 hours, and left still for 30 minutes. The separated water layer of the lower layer was removed, and the water washing of the reaction liquid was repeated until the washing liquid became neutral. Next, 158 parts of aromatic amine resins (A-1) represented by the above formula (2) were obtained by distilling off excess aniline and toluene from the oil layer under heating and decompression using a rotary evaporator. The amine equivalent of the aromatic amine resin (A-1) was 186.1 g/eq, and the softening point was 58.8°C. According to GPC analysis (RI), n=1 body was 62.5 area %. The GPC diagram is shown in Figure 1.

[Synthesis Example 2] Synthesis of Maleimide Resin (M-1) 73.5 parts of maleic anhydride, 126 parts of toluene, 1.86 parts of methanesulfonic acid, and N-methyl-2-pyrrole were placed in a flask equipped with a thermometer, a cooling pipe, a Dean Stark azeotropic distillation trap, and a stirrer. 12.6 parts of pyridones were heated and refluxed. Next, the resin solution obtained by dissolving 93 parts of aromatic amine resin (A-1) in 55.8 parts of toluene was dripped over 4 hours, maintaining a reflux state. During this period, the condensation water and toluene azeotroped under reflux conditions are cooled/separated in the Dean Stark azeotropic distillation trap, the toluene as an organic layer is returned to the system, and the water is discharged to the outside of the system . After the dropwise addition of the resin solution was completed, the reaction was performed for 10 hours while maintaining the reflux state while performing a dehydration operation. After completion of the reaction, washing with water was repeated four 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 at 70°C or lower. Next, 2 parts of methanesulfonic acid was added, and the reaction was carried out for 4 hours in a heated reflux state. After the completion of the reaction, washing with water was repeated 3 times until the washing water became neutral, and then the water was removed from the system by the azeotropy of toluene and water under heating and decompression at a temperature of 70°C or lower, and then distillation was carried out under heating and decompression. After removing the solvent until the toluene has a resin concentration of about 70% to 80%, toluene is added to adjust the resin concentration to 60%. Thereby, the maleimide solution (V-1) containing the maleimide (M-1) of the present invention was obtained. According to GPC analysis (RI), the obtained maleimide resin (M-1) had 57.4 area% of n=1 body, 21.3 area% of n=2 body, and 21.3 area% of n=3 body or more. According to HPLC analysis (225 nm), the alignment ratio in the n=1 body (ortho-ortho/para-para/ortho-para) was 32.0%/25.4%/42.6%. In addition, the softening point was 115.5°C, and the viscosity was 6.0 Pa·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 proportions shown in Table 1, toluene was added to make the resin solid content 50%, and then the mixture was heated and mixed at 70° C. for 1 hour. This makes varnish. The solubility and compatibility of the resin at this time were visually confirmed and evaluated under the conditions described later. The results are shown in Table 1. Furthermore, dicumyl peroxide (DCP (dicumyl peroxide), a chemical drug Nouryon) as a hardening accelerator was dissolved in the varnish. A curable resin composition was prepared by heating the varnish in which the hardening accelerator was dissolved by a vacuum dryer at 80°C for 30 minutes and at 120°C for 1 hour. The obtained curable resin composition was sandwiched between copper foils, and was cured at 220° C. for 2 hours by applying a pressure of 1 MPa under vacuum. The curability at this time was confirmed and evaluated under the conditions described later. Table 1 shows the results of various measurements of the obtained hardened product.

Solubility Judgment Conditions: 〇･･･No precipitation in solution ×･･･Precipitation in solution Compatibility criteria: 〇･･･Compatible ×･･･Incompatibility (phase separation) 220℃ curability judgment condition: 〇･･･Cured product can be obtained ×･･･No hardened product obtained (hardened product is brittle and cannot be taken out)

･M-1 (The solvent obtained in Synthesis Example 2 was distilled off by heating and reducing pressure) ･MIR-3000 (The solvent of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd.) is distilled off 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 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Mn: 1200

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Maleimide compound M-1 50 25 10 5 50 75 100 MIR-3000 50 BMI-70 50 BMI-2300 50 Compounds with a polyphenylene ether structure SA-9000-111 50 75 90 95 25 100 50 50 50 OPE-2st 1200 50 Equivalent of SA-9000-111 relative to M-11 equivalent 0.2 0.7 2 4.2 0.5 0.1 - - - - - hardening accelerator DCP 1 1 1 1 1 1 1 1 1 1 1 Solvent Solubility Toluene 〇 〇 〇 〇 〇 〇 〇 〇 〇 × × compatibility 〇 〇 〇 〇 〇 〇 × 〇 × 220°C hardening 〇 〇 〇 〇 〇 〇 〇 × 〇 〇 〇 heat resistance Tg[℃] 255.9 237.9 211.9 209.3 283.3 276.6 280.3 - 213.6 257.1 235.5 Elasticity coefficient reduction temperature [℃] 191.8 192.2 159.0 151.3 233.6 204.4 158.1 - 191.0 218.5 210.4 Mechanical strength Tensile modulus of elasticity [GPa] 2.12 1.77 1.92 1.96 1.83 2.64 2.98 - 1.96 1.94 2.1 Maximum point stress [MPa] 64.1 71.8 60.8 32.3 73 46.3 36.4 - 58.1 41.6 36.3 Maximum point elongation [%] 3.69 4.79 4.02 2.47 1.67 1.99 1.92 - 3.20 2.56 2.05 Copper foil tensile strength [N∕mm] 0.45 0.54 0.51 0.35 0.38 0.33 0.24 - 0.38 0.51 0.32 Water absorption properties Water absorption [%] 0.33 0.05 0.11 0.08 0.22 0.51 0.65 - 0.21 0.78 0.88 Dielectric Properties (10 GHZ) Dielectric constant Dk[-] 2.657 2.475 2.479 2.487 2.524 2.697 2.573 - 2.717 2.595 2.727 Dielectric constant Dk[-] after water absorption for 24 h 2.692 2.493 2.492 2.501 2.554 2.733 2.672 - 2.753 2.666 2.838 Dielectric loss tangent Df[-] 0.0026 0.0029 0.0028 0.0030 0.0028 0.0023 0.0017 - 0.0029 0.0026 0.0022 Dielectric loss tangent Df[-] after water absorption for 24 h 0.0038 0.0036 0.0032 0.0033 0.0040 0.0045 0.0043 - 0.0043 0.0062 0.0074

In Examples 1 to 5, it was confirmed that the solvent solubility and compatibility were good, the curing reaction proceeded well at 220° C. for 2 hours, and the heat resistance, copper foil peel strength, moisture resistance, and dielectric properties were excellent. In Comparative Example 1, since a large amount of the maleimide compound (M-1) was used, it was confirmed that the water absorption rate and the dielectric properties were high (poor). When the maleimide compound (M-1) was used alone as in Comparative Example 2, it was confirmed that the heat resistance and the dielectric loss tangent were good, but the copper foil had low peel strength and high water absorption, so water was absorbed. The resulting dielectric loss tangent also deteriorates. When the polyphenylene ether compound having an unsaturated double bond was used alone as in Comparative Example 3, it was not cured under the curing conditions of 220° C. and 2 hours. When other maleimide resins were used as in Comparative Examples 4 to 6, the solvent solubility and compatibility were poor, and the dielectric properties and the dielectric properties after water absorption were high (poor).

none

FIG. 1 is a graph of gel permeation chromatography (GPC) of Synthesis Example 1. FIG. FIG. 2 is a GPC chart of Synthesis Example 2. FIG.

Claims (7)

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

In formula (1), R represents a hydrogen atom or a methyl group; m represents an integer of 0 to 3; n is a repeating number, and the average value thereof is 1<n<5. A curable resin composition containing a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond in an amount of 1 equivalent relative to the component (A) , the component (B) is 0.20 equivalent to 4.2 equivalent,

In formula (1), R represents a hydrogen atom or a methyl group; m represents an integer of 0 to 3; n is a repeating number, and the average value thereof is 1<n<5. The curable resin composition according to claim 1 or 2, wherein the component (B) is a polyphenylene ether compound having a (meth)acrylic group. The curable resin composition according to any one of claims 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 the average value thereof is 1<n<10. The curable resin composition according to any one of claims 1 to 4, further comprising a hardening accelerator. A prepreg obtained by holding the curable resin composition according to any one of claims 1 to 5 in a sheet-like fiber base material. A hardened product obtained by hardening the curable resin composition according to any one of claims 1 to 5, or the prepreg according to claim 6.

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