KR20230150253A - Curable resin composition, prepreg and its cured product - Google Patents

Abstract

The present invention provides a curable resin composition and a cured product thereof that exhibit excellent heat resistance, copper foil peel strength, dielectric properties, and moisture resistance.
It contains a maleimide compound (A) represented by the following formula (1) and a polyphenylene ether compound (B) having an unsaturated double bond, and the weight ratio of component (A) and component (B) is 50/50 to 5. /95 curable resin composition.
[Formula 1]

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

Description

Curable resin composition, prepreg and its cured product

The present invention relates to curable resin compositions, prepregs, and cured products thereof, and to electrical and electronic components such as semiconductor sealants, printed wiring boards, and build-up laminates, lightweight high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D materials. Suitable for printing purposes.

Recently, the required characteristics of laminated boards carrying electrical and electronic components have become wider and more sophisticated due to the expansion of their fields of use. For example, conventionally, semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with advanced processing capabilities, such as CPUs, are increasingly mounted on laminated boards made of polymer materials. As the speed of devices such as CPUs progresses and clock frequencies increase, signal propagation delay and transmission loss become problems, and lower dielectric constants and lower dielectric loss tangents are required for wiring boards.

In terms of the development of communication technology, the momentum of 5G has recently increased, and communication devices using not only Sub6 but also quasi-millimeter waves and millimeter waves above 10GHz, especially above 28GHz, are expected to increase explosively, and high-frequency waves are used in base stations, antennas, and communication devices. There is a need for substrate materials that correspond to . In these substrate materials, high dielectric properties (especially dielectric loss tangent) are considered important in order to avoid lowering the transmission speed, and materials that can be used stably in these areas are required.

In addition, with the recent spread of mobile electronic devices such as mobile phones, precision electronic devices have come to be used and carried in outdoor environments or in close proximity to the human body, so resistance to external environments (particularly moist and heat-resistant environments) is considered necessary. Additionally, in the automotive field, electronics is rapidly progressing and precision electronic devices are sometimes placed near engines, which requires higher levels of heat and moisture resistance.

Wiring boards using BT resin, which is a resin using a combination of a bisphenol A type cyanate ester compound and a bismaleimide compound, such as those shown in Patent Document 1, have been widely used as high-performance wiring boards in the past because of their excellent heat resistance, chemical resistance, and dielectric properties. Improvements are needed to provide additional high-performance response such as .

Meanwhile, maleimide resins available on the market have significantly improved heat resistance compared to epoxy resins, etc., which have been conventionally used for the above-mentioned applications, and exhibit excellent dielectric properties in the high frequency range. However, maleimide resins with high heat resistance have low moisture resistance. Because it is low and rigid, it has the disadvantage of being brittle and having low adhesion to copper foil.

In contrast, maleimide resins such as those in Patent Documents 2 and 3 have also been developed, but they cannot be said to be sufficient yet.

In addition, a composition containing a maleimide resin and a propenyl group-containing phenolic resin, such as in Patent Document 4, has been proposed, but in addition, the dielectric properties are not sufficient because phenolic hydroxyl groups that are not involved in the reaction remain during the curing reaction. There is a problem with the high absorption rate.

Patent Document 1: Japanese Special Public Service Office Publication No. 54-30440 Patent Document 2: Japanese Patent Application Publication No. 3-100016 Patent Document 3: Japanese Patent No. 5030297 Patent Document 4: Japanese Patent Application 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 was made in consideration of this situation, and its purpose is to provide a curable resin composition and a cured product thereof that exhibit excellent heat resistance, copper foil peel strength, dielectric properties, and moisture resistance.

The present inventors have conducted extensive research to solve the above problems, and as a result, a cured product of a curable resin composition composed of a maleimide compound having a specific structure and a polyphenylene ether compound having an unsaturated double bond has excellent heat resistance, copper foil peel strength, and dielectric properties. , discovered that it had excellent moisture resistance, and completed the present invention.

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

[One]

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

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

[2]

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

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

[3]

The curable resin composition according to the preceding 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 preceding 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 equation (2), n is the number of repetitions, and its average value is 1 < n < 10.)

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

[5]

The curable resin composition according to any one of the preceding items [1] to [4], further comprising a curing accelerator.

[6]

A prepreg comprising the curable resin composition according to any one of the preceding items [1] to [5] in a sheet-like fiber substrate.

[7]

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

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

[Figure 1] GPC chart of Synthesis Example 1.
[Figure 2] GPC chart of Synthesis Example 2.

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

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

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

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

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

In the above formula (1), when n = 1, the solubility in solvents is low, and when n is 5 or more, the flow properties during molding become poor and the properties as a cured product cannot be sufficiently exhibited.

Component (A) preferably has a molecular weight distribution, and in the formula (1) above, the content of n = 1 body as determined by GPC analysis (RI) is preferably 98 area% or less, more preferably 20 to 90 area%. %, more preferably 30 to 80 area %, particularly preferably 40 to 80 area %. If the n=1 content is 98 area% or less, heat resistance becomes good. Additionally, crystallinity decreases and solvent solubility improves. On the other hand, if the lower limit of n = 1 body is 20 area% or more, the viscosity of the resin solution decreases and the impregnability becomes good. In addition, since it is a solid and the solvent can be removed at low temperature when taken out, self-polymerization is unlikely to occur, making handling easier.

By increasing the ratio of asymmetric structures with different orientations to maleimide groups, component (A) improves solvent solubility and can improve the dielectric properties of the cured product. The orientation ratio in the n = 1 body of the above formula (1) can be obtained from HPLC analysis (225 nm), and the ortho-para body is preferably 30 area % or more and less than 60 area % of the total amount of n = 1 body, and 35 area %. It is more preferable that it is less than 55 area%, and it is especially preferable that it is 40 area% or more and less than 55 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. Additionally, the melt viscosity at 150°C is 0.05 to 100 Pa·s, preferably 0.1 to 40 Pa·s.

Hereinafter, the manufacturing method of component (A) will be described, but it is not limited to this manufacturing 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 the number of repetitions, and the average value is 1 < n < 5.)

The method for producing the aromatic amine resin represented by the above formula (3) is not particularly limited. For example, in Patent Document 5, aniline and m-diisopropenylbenzene or m-di(α-hydroxyisopropyl)benzene are mixed in an acidic form. By reacting at 180 to 250°C in the presence of a catalyst, the n=1 body in the above formula (3) is obtained as the main component. Among the n=1 compounds, there are compounds with a symmetrical structure with the same orientation to the two aniline molecules, such as 1,3-bis(p-aminocumyl)benzene and 1,3-bis(o-aminocumyl)benzene, or 1-(o- It contains three isomers of asymmetric compounds with different orientations to the two aniline molecules, such as aminocumyl)-3-(p-aminocumyl)benzene. In addition, n=2 to 5 compounds are also produced as secondary components, but in Patent Document 5, these are purified by crystallization to obtain 1,3-bis(p-aminocumyl)benzene with a purity of 98%. Additionally, in Patent Document 6, 1,3-bis(p-aminocumyl)benzene is maleimized to form N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p -Phenylene)bismaleimide is synthesized to obtain a crystal product, but heating is required to dissolve it in a solvent, and if left at room temperature after heating, crystals will precipitate in a few hours. Therefore, even when adjusting the resin composition, crystals may precipitate, and N,N'-(1,3-phenylene-di-(2,2-propylidene)-di-p-phenylene)bismaleide The higher the concentration of mead, 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 to adhere the resin. However, if crystals precipitate, impregnation becomes impossible. Meanwhile, if the temperature is raised to maintain the dissolved state, the reaction of the composition becomes faster and the varnish becomes varnished. The housework time becomes shorter.

When synthesizing the aromatic amine resin represented by the above formula (3), the acidic catalyst used is acidic catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, and methanesulfonic acid. I can hear it. 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 types. The amount of catalyst used is preferably 1 to 12% by weight, more preferably 1 to 10% by weight, and particularly preferably 1 to 7% by weight, based on 100% by weight of aniline used. If it is more than 12% by weight, the desired catalyst amount is There are few compounds with an asymmetric structure, and compounds with a symmetric structure are formed with priority. On the other hand, if it is less than 1%, it is not preferable because not only does the progress of the reaction slow down, but the reaction may not be completed in some cases.

If necessary, the reaction may be performed using an organic solvent such as toluene or xylene, or may be performed without a solvent. For example, after adding an acidic catalyst to a mixed solution of aniline and a solvent, if the catalyst contains water, it is preferable to remove the water from the system by azeotrope. After that, diisopropenylbenzene or di(α-hydroxyisopropyl)benzene is added, and the temperature is raised while excluding the solvent from the system, and the temperature is raised to 140 to 190°C, preferably 160 to 190°C for 5 to 50 hours. , Preferably the reaction is performed for 5 to 30 hours. If the reaction temperature is too high, the asymmetric structure recombines after formation and the symmetric structure takes precedence, making it impossible to achieve the desired solvent solubility and electrical properties. When di(α-hydroxyisopropyl)benzene is used, water is produced as a by-product, so it is removed from the system while azeotropically mixing with the solvent when the temperature is raised. After completion of the reaction, the acid catalyst is neutralized with an aqueous alkaline solution, a non-water-soluble organic solvent is added to the oil layer, and water washing is repeated until the waste water becomes neutral, and then the solvent and excess aniline derivative are removed by heating under reduced pressure. When activated clay or ion exchange resin is used, the catalyst is removed by filtering the reaction solution after completion of the reaction.

Additionally, since diphenylamine is produced as a by-product depending on the reaction temperature and type of catalyst, it is preferable to remove it as necessary. The diphenylamine derivative is removed to 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.2% by weight or less under high temperature and vacuum or using means such as steam distillation.

[Method for producing maleimide resin]

Component (A) is obtained by adding or dehydrating the aromatic amine resin represented by the formula (3) obtained through the above process and maleic acid or maleic anhydride (hereinafter also referred to as “maleic anhydride”) in the presence of a solvent and a catalyst. Obtained through condensation reaction.

The solvent used in the reaction is preferably a non-water-soluble solvent because water generated during the reaction needs to be removed from the system. 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, and methyl isobutyl ketone. , ketone-based solvents such as cyclopentanone, etc., but it is not limited to these, and two or more types may be used together.

Additionally, in addition to the above-mentioned water-insoluble solvent, an aprotic polar solvent can also be used together. For example, dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, etc., two or more types. You can use it together. When using an aprotic polar solvent, it is preferable to use one with a higher boiling point than the non-aqueous solvent used together.

Additionally, the catalyst used in the reaction is an acidic catalyst and is not particularly limited, but examples include p-toluenesulfonic acid, hydroxy-p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, and phosphoric acid. The amount of the acid catalyst used is usually 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the aromatic amine resin.

For example, the aromatic amine resin represented by the above formula (3) is dissolved in toluene and N-methyl-2-pyrrolidone, maleic anhydride is added thereto to produce amic acid, and then p-toluenesulfone is added. The reaction is carried out by adding an acid and removing the produced water from the system under reflux conditions.

Alternatively, maleic anhydride is dissolved in toluene, and an N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the above formula (3) is added under stirring to produce amic acid, and then p-toluenesulfonic acid is added. The reaction is carried out under reflux conditions while removing the produced water from the system.

Alternatively, maleic anhydride is dissolved in toluene, p-toluenesulfonic acid is added, and while stirring and refluxing, the N-methyl-2-pyrrolidone solution of the aromatic amine resin represented by the above formula (3) is added dropwise, and azeotroped halfway. The water that comes out is removed from the system, and the toluene is returned to the system to carry out the reaction (above, first stage reaction).

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

In order to reduce the amount of unclosed amic acid, water is added to the reaction solution after the maleimidization reaction listed above, and the resin solution layer and aqueous layer are separated, and excess maleic acid or maleic anhydride, aprotic polar solvent, and catalyst are added. Since these substances are dissolved in the water layer, they are separated and removed, and the same operation is repeated to thoroughly remove excess maleic acid, maleic anhydride, aprotic polar solvent, and catalyst. The catalyst is added again to the maleimide resin solution in the organic layer from which excess maleic acid, maleic anhydride, aprotic polar solvent, and catalyst have been removed, and the dehydration ring-closure reaction of the remaining amic acid is performed again under heated reflux conditions to produce a low acid value. A maleimide resin solution is obtained (above, second stage reaction).

The time for the re-dehydration ring-closure reaction is usually 1 to 5 hours, preferably 1 to 3 hours, and the aprotic polar solvent described above may be added as necessary. After completion of the reaction, it is cooled, and washing with water is repeated until the washing water becomes neutral. Afterwards, the water may be removed by azeotropic dehydration under heating and reduced pressure, and then the solvent may be distilled off or a separate solvent may be added to adjust the resin solution to a desired concentration. The solvent may be completely distilled off and taken out as a solid resin. do.

Next, component (B) is explained.

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 component (B) include (meth)acrylic group, styrene group, allyl group, vinyl group, and methallyl group, and it is preferable that it is a (meth)acrylic group. Commercially available products include SA-9000-111 (manufactured by Sabic, a polyphenylene ether compound having a methacryl group) represented by the following formula (2) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound having a styrene group) represented by the formula (4) below. polyphenylene ether compounds) and the like. In particular, from the viewpoint of dielectric properties, compounds represented by the following formula (2) are preferable.

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

(In equation (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 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. When the molecular weight is 500 or more, the heat resistance of the cured product improves. If the molecular weight is 5000 or less, the melt viscosity is lowered, sufficient fluidity can be obtained, and moldability becomes good. Additionally, because reactivity is improved, the curing time can be shortened and the heat resistance of the cured product is also improved. The weight average molecular weight can be specifically measured using gel permeation chromatography or the like.

Component (B) can impart radical polymerization by reacting a polyphenylene ether compound with a compound having an unsaturated double bond such as methacryl chloride, acrylic chloride, or chloromethylstyrene.

The polyphenylene ether compound may be obtained through a polymerization reaction, or may be obtained 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. For example, the redistribution reaction is carried out by heating a high molecular weight polyphenylene ether compound in the presence of a phenol compound and a radical initiator in a solvent such as toluene. The polyphenylene ether compound obtained through the redistribution reaction in this way is preferable because it can maintain higher heat resistance because it has hydroxyl groups derived from phenolic compounds that contribute to hardening at both ends of the molecular chain. Additionally, polyphenylene ether compounds obtained through polymerization reactions are preferable because they exhibit excellent fluidity.

The molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions, etc. in the case of a polyphenylene ether compound obtained through a polymerization reaction. Additionally, in the case of polyphenylene ether compounds obtained through redistribution reaction, the molecular weight can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it is conceivable to adjust the amount of the phenolic compound used in the redistribution reaction. In other words, the larger the amount of the phenol-based compound, the lower the molecular weight of the polyphenylene ether compound obtained.

Additionally, specific examples of polyphenylene ether compounds include poly(2,6-dimethyl-1,4-phenylene ether). That is, in the case of component (B) obtained by redistribution reaction, a polyphenylene ether compound obtained using poly(2,6-dimethyl-1,4-phenylene ether) as a high molecular weight polyphenylene ether compound, etc. I can hear it. In addition, the phenolic compound used in the redistribution reaction is not particularly limited, but examples include polyfunctional phenolic compounds having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolak, etc. It is preferably used. These may be used individually, or two or more types may be used in combination.

The weight ratio of component (A) and 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, and even more preferably 25. /75 to 5/95, and particularly preferably 25/75 to 10/90. Additionally, the functional group equivalent ratio of component (A) and component (B) is preferably 0.2 to 4.2 equivalents of component (B) relative to 1 equivalent of component (A), more preferably 0.5 to 4.2 equivalents, and further. Preferably it is 0.7 to 4.2 equivalents, and particularly preferably 0.7 to 2.0 equivalents. If the component (B) is less than 0.2 equivalents, the maleimide group increases, causing the water absorption properties to deteriorate and the cured product to become brittle, thereby lowering the copper foil peel strength. On the other hand, when the amount of component (B) is more than 4.2 equivalents, the crosslinking density decreases and heat resistance deteriorates.

In addition to component (A) and component (B), any known resin material can be used in the curable resin composition of the present invention. Specifically, phenol resin, epoxy resin, amine resin, activated alkene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, propenyl resin, methallyl resin, activated ester resin, etc., You may use it one type or may use it in combination. Additionally, maleimide compounds other than component (A) may be used together.

Phenol resin, epoxy resin, amine resin, activated alkene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, and activated ester resin can be used as shown below, but are not limited to these. .

Phenol resin: Phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes and forms. Polycondensates with aldehydes (benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), phenols and various diene compounds (dicyclopentadiene, terpenes) , polymers with vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones (acetone) , methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and Substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), or substituted phenyls Phenolic resins obtained by polycondensation with (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.), bisphenols, and Polycondensates of various aldehydes, polyphenylene ether.

Epoxy resin: Glycidyl ether-based epoxy resin obtained by glycidylating the above phenol resins, alcohols, etc., 4-vinyl-1-cyclohexene diepoxide or 3,4-epoxycyclohexylmethyl-3,4'- Alicyclic epoxy resins such as epoxycyclohexanecarboxylate, glycidylamine-based epoxy resins such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol, Glycidyl ester-based epoxy resin.

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

Active alkene-containing resin: Polycondensate of the above phenol resins and active alkene-containing halogen-based compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, etc.), active alkene-containing phenols (2-allylphenol, 2-propenyl) Phenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogenated compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1, Polycondensate of 4-bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), epoxy Polycondensation of resins or alcohols and substituted or unsubstituted acrylates (acrylates, methacrylates, etc.), maleimide resins (4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenyl Lenbismaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebis Maleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimide) Midphenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene).

Isocyanate resin: p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenyl Aromatic diisocyanates such as methane diisocyanate and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; Polyisocyanates such as one or more biuret forms of isocyanate monomers or isocyanate forms obtained by trimerizing the above diisocyanate compounds; Polyisocyanate obtained by urethanization reaction of the above isocyanate compound and polyol compound;

Polyamide resin: Amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanalactam, ω-laurolactam) ) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, Tetradecanediamine, pentadecanediamine, hepsadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosane diamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diamino Aliphatic diamines such as octane; Alicyclic diamines such as cyclohexanediamine, bis-(4-aminocyclohexyl)methane, and bis(3-methyl-4-aminocyclohexyl)methane; Aromatic diamines such as xylylenediamine, 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, and dodecanedioic acid; terephthalic acid, isophthalic acid, etc. , aromatic dicarboxylic acids such as 2-chloroterephthalic acid, 2-methyl terephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; alicyclic acids such as cyclohexanedicarboxylic acid, etc. A polymer made mainly of one or more types selected from the group dicarboxylic acids; dialkyl esters of these dicarboxylic acids, and mixtures of dichlorides).

Polyimide resin: diamine above and tetracarboxylic dianhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)- 3-Methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenone Tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1- Ethylidene-4,4'-diphthalic dianhydride, 2,2'-Propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3 -trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4, 4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride Water, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3) ,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 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 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-perylene tetracarboxylic dianhydride, 2,3,6,7-anthracene Tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2 ,3,4-Cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic 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-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Boxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis(cyclo Hexane-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]octo-7- N-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'-biphenylbis(trimellitic acid monoester acid anhydride), 9,9'- Polycondensation product with bis(3,4-dicarboxyphenyl)fluorene dianhydride.

Cyanate ester resin: A cyanate ester compound obtained by reacting a phenol resin with a cyanide halide. Specific examples include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyanate biphenyl, and 2,2'-bis. (4-cyanatephenyl)propane, bis(4-cyanatephenyl)methane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2'-bis(3,5-dimethyl-4- Cyanatephenyl)propane, 2,2'-bis(4-cyanatephenyl)ethane, 2,2'-bis(4-cyanatephenyl)hexafluoropropane, bis(4-cyanatephenyl)sulfone, bis (4-cyanate phenyl)thioether, phenol novolaxyanate, and those obtained by converting the hydroxyl group of phenol/dicyclopentadiene cocondensate to cyanate group, etc., but are not limited to these.

Additionally, the cyanate ester compound whose synthesis method is described in Japanese Patent Application Laid-Open No. 2005-264154 is particularly preferable as a cyanate ester compound because it has excellent low hygroscopicity, flame retardancy, and dielectric properties.

Cyanate resin trimerizes the cyanate group as needed to form a sym-triazine ring, including zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, lead acetylacetonate, A catalyst such as dibutyltin maleate may also be contained. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 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 per molecule can be used as a curing agent for curable resins such as epoxy resins. As the active ester-based curing agent, compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are preferable. The active ester-based curing agent 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 hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound is preferable. do.

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 phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. , p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxynaphthalene Hydroxybenzophenone, tetrabenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two phenol molecules with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylate of phenol novolak, and benzoyl phenol novolac. and active ester compounds containing cargo. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferable. “Dicyclopentadiene-type diphenol structure” refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC- 8000H-65TM”, “EXB-8000L-65TM”, “EXB-8150-65T” (manufactured by DIC); As an active ester compound containing a naphthalene structure, "EXB9416-70BK" (manufactured by DIC); As an active ester compound containing an acetylated product of phenol novolac, "DC808" (manufactured by Mitsubishi Chemical Corporation); As active ester compounds containing the benzoylate of phenol novolac, “YLH1026”, “YLH1030”, and “YLH1048” (manufactured by Mitsubishi Chemical Corporation); As an active ester-based curing agent that is an acetylated product of phenol novolac, “DC808” (manufactured by Mitsubishi Chemical Corporation); “EXB-9050L-62M” manufactured by DIC as an active ester-based curing agent containing a phosphorus atom; etc. can be mentioned.

The curability of the curable resin composition of the present invention can be further improved by using a curing accelerator (curing catalyst) in combination. As a specific example of a curing accelerator that can be used, it is preferable to use a radical polymerization initiator for the purpose of promoting self-polymerization of a radically polymerizable curable resin such as olefin resin or maleimide resin or radical polymerization with other components. As radical polymerization initiators, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis-(t-butylperoxyisopropyl)- Dialkyl peroxides such as benzene, peroxyketals such as t-butyl peroxybenzoate, 1,1-di-t-butyl peroxycyclohexane, α-cumyl peroxyneodecanoate, t-butyl Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t -Butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate Alkyl peresters such as oxybenzoate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropyl carbonate, 1,6-bis(t -Peroxycarbonates such as butylperoxycarbonyloxy)hexane, organic peroxides such as t-butylhydroperoxide, cumene hydroperoxide, t-butylperoxyoctoate, and lauroyl peroxide, or azobisisobutyrate. Known curing accelerators of azo compounds such as nitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) may be mentioned. It is not particularly limited to these. Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, peroxycarbonates, etc. are preferable, and dialkyl peroxides are more preferable. The amount of the radical polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of radical polymerization initiator used is large, the dielectric properties of the cured product deteriorate.

In the curable resin composition of the present invention, there is no problem even if a curing accelerator other than the radical polymerization initiator is added or used in combination, if necessary. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, and 1,8 -tertiary amines such as diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethyl Quaternary ammonium salts such as ammonium salts and hexadecyltrimethyl ammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts (the counter ions of quaternary salts are halogen, Organic acid ions, hydroxide ions, etc. are not specifically designated, but organic acid ions and hydroxide ions are particularly preferred.), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, myristic acid). and transition metal compounds (transition metal salts) such as zinc compounds such as zinc) and zinc phosphate esters (octyl zinc phosphate, zinc stearyl phosphate, etc.). The amount of the curing accelerator used is 0.01 to 5.0 parts by weight based on 100 parts by weight of the curable resin composition.

Additionally, 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 of a reactive type or an addition type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dicxylenyl phosphate, and 1,3-phenylenebis (dic phosphoric acid esters such as sylexylenyl phosphate), 1,4-phenylenebis(dicxylenyl phosphate), and 4,4'-biphenyl (dicxylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide phosphanes such as; Phosphorus-containing epoxy compounds obtained by reacting an epoxy resin with the active hydrogen of the phosphanes, phosphorus, etc. are included, but phosphoric acid esters, phosphenes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dicylate) Nylphosphate), 1,4-phenylenebis(dicylenylphosphate), 4,4'-biphenyl(dicxylenylphosphate) or phosphorus-containing epoxy compounds are particularly preferred. 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 is insufficient, and if it is 0.6 or more, there is a risk of adversely affecting the hygroscopicity 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 a light stabilizer, a hindered amine light stabilizer, especially HALS, is suitable. There is no particular limitation on HALS, but representative examples include dibutylamine, 1,3,5-triazine, N, N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1, Polycondensate of 6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, 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-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}, bis( 1,2,2,6,6-pentamethyl-4-piperidyl)[{3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl}methyl]butylmalonate, bis( 2,2,6,6-tetramethyl)-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyl) Roxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis. (1,2,2,6,6-pentamethyl-4-piperidyl) and the like. Only one type of HALS may be used, or two or more types may be used together.

Additionally, a binder resin may be added to the curable resin composition of the present invention as needed. Binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenolic resins, epoxy-NBR resins, polyamide resins, polyimide resins, silicone resins, etc. It is 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, more preferably 0.05 to 20 parts by mass, based on 100 parts by mass of the resin component.

Furthermore, the curable resin composition of the present invention may optionally contain fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, Powders such as forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide, asbestos, glass powder, or inorganic fillers made of these in spherical or crushed form can be added. In addition, especially for semiconductor sealing. When obtaining a curable resin composition, the amount of the inorganic filler used is usually in the range of 80 to 92% by mass, preferably 83 to 90% by mass, in the curable resin composition.

Furthermore, known additives can be blended into the curable resin composition of the present invention as needed. Specific examples of additives that can be used include polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and fillers such as silane coupling agents. surface treatment agents, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green. The blending amount of these additives is preferably in the range of 1,000 parts by mass or less, more preferably 700 parts by mass or less, based on 100 parts by mass of the resin component.

The curable resin composition of the present invention is obtained by uniformly mixing the above components at a predetermined ratio, usually pre-cured at 130 to 180°C for 30 to 500 seconds, and further at 150 to 200°C for 2 to 15 hours. By post-curing, sufficient curing reaction proceeds and the cured product of the present invention is obtained. Additionally, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like and cured after removing the solvent.

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 that require moisture resistance, heat resistance, high adhesion, low dielectric constant, and low dielectric loss tangent. Specifically, it is useful as a material for all electrical and electronic components, such as insulating materials, laminated boards (printed wiring boards, BGA boards, build-up boards, etc.), sealing materials, and resists. In addition to molding materials and composite materials, it can also be used in fields such as paint materials, adhesives, and 3D printing. Particularly in semiconductor sealing, solder reflow resistance is beneficial.

A semiconductor device has been sealed with the curable resin composition of the present invention. Examples of semiconductor devices include DIP (Dual Inline Package), QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (Small Outline Package), and TSOP (Small Outline Package). , TQFP (Sink Ward Flat Package), etc.

The method for producing the curable resin composition of the present invention is not particularly limited, but as described above, each component may be dispersed or dissolved in a solvent or the like, mixed uniformly, and the solvent may be distilled off as necessary to prepare or prepolymerize the composition. For example, component (A) and component (B) are prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, in addition to components (A) and (B), curing agents such as epoxy resins, amine compounds, maleimide compounds, cyanate ester compounds, phenol resins, and acid anhydride compounds and other additives may be added to prepolymerize. For mixing or prepolymerization of each component, for example, an extruder, kneader, roll, etc. is used in the absence of a solvent, and a reaction pot with a stirring device is used in the presence of a solvent.

As a method of uniformly mixing without using solvents, etc., kneading is performed using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100°C to form a uniform curable resin composition. . The obtained curable resin composition is pulverized and then molded into a cylindrical tablet shape using a molding machine such as a tablet machine, or made into a granular powder or powder-shaped molded body, or these compositions are melted on a surface support to form a cylindrical tablet shape of 0.05 mm to 10 mm. It can also be molded into a thick sheet shape and used as a curable resin composition molded body. The obtained molded body becomes a non-sticky molded body at 0 to 20°C, and fluidity and curability are hardly reduced even when stored at -25 to 0°C for more than a week.

The obtained molded body can be molded into a cured 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 produce a varnish-like composition (hereinafter also simply referred to as varnish). If necessary, the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, etc. to make a varnish and form a glass. The prepreg obtained by impregnating a base material such as fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and then heating and drying the prepreg can be formed into a cured product of the curable resin composition of the present invention by heat press molding. The solvent at this time is usually used in an amount that accounts for 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 solvent amount is less than this range, the varnish viscosity increases and workability deteriorates, and if the solvent amount is large, it causes voids to form in the cured product. Additionally, if it is a liquid composition, a curable resin material containing carbon fiber can be obtained as is, for example, by the RTM method.

Additionally, the curable composition of the present invention can also be used as a modifier for a film-like composition. Specifically, it can be used to improve flexibility in the B-stage. This film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of the present invention as the curable resin composition varnish on a release film, removing the solvent under heating, and then performing B-staging. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

The curable resin composition of the present invention can be obtained by heating and melting, lowering the viscosity, and impregnating reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber 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, as well as fibers made of inorganic substances other than glass and polypara. Phenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Corporation), wholly aromatic polyamide, polyester; and organic fibers such as polyparaphenylenebenzoxazole, polyimide, and carbon fiber, but are not particularly limited to these. The shape of the base material is not particularly limited, but examples include woven fabric, non-woven fabric, roving, and chopped strand mat. In addition, plain weave, mat weave, twill weave, etc. are known as weaving methods for woven fabrics, and these known methods can be appropriately selected and used depending on the intended use or performance. Additionally, a woven fabric that has been opened and treated or a glass woven fabric that has been surface treated with a silane coupling agent or the like is preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Additionally, a prepreg can be obtained by impregnating reinforcing fibers with the varnish and heating and drying them.

The laminated board of this embodiment is provided with one or more sheets of the above prepreg. The laminated board is not particularly limited as long as it has one or more prepregs, and may have any other layers. As a manufacturing method for a laminated board, generally known methods can be appropriately applied and are not particularly limited. For example, when forming a metal foil-clad laminate, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used, and a laminate can be obtained by laminating the prepregs and heat-pressing molding. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300°C, and more preferably 120 to 270°C. In addition, the pressing pressure is not particularly limited, but if the pressing pressure is too large, it is difficult to adjust the solid content of the resin of the laminate and the quality will not be stable, and if the pressure is too small, bubbles or adhesion between laminates will deteriorate, so 2.0 to 5.0 MPa is preferable. And 2.5 to 4.0 MPa is more preferable. The laminated board of this embodiment can be suitably used as a laminated board with metal foil described later by providing a layer made of metal foil.

After cutting the prepreg into the desired shape and laminating it with copper foil, etc. as necessary, the curable resin composition is heat-cured while applying pressure to the laminate using a press molding method, an autoclave molding method, a sheet winding molding method, etc., thereby producing a laminate for electrical and electronic use (printed). wiring board) or carbon fiber reinforcement.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials, and paints. Since the cured product of the curable resin composition described in the present invention exhibits excellent heat resistance and dielectric properties, it can be used in electrical and electronic components such as sealing materials for semiconductor devices, sealing materials for liquid crystal display devices, sealing materials for organic EL devices, printed wiring boards, and build-up laminates. It is suitable for use in lightweight, high-strength structural composite materials such as carbon fiber reinforced plastic and glass fiber reinforced plastic.

[Example]

Hereinafter, the present invention will be described in detail through examples and comparative examples. In addition, “part” and “%” in the text represent “part by weight” and “% by weight”, respectively. Softening point and melt viscosity were measured by the following methods.

ㆍSoftening point: Measured in accordance with JIS K-7234

ㆍMel viscosity: ICI melt viscosity (150°C) is measured by the corn plate method, and the unit is Pa·s.

ㆍGPC (Gel Permeation Chromatography) Analysis

Maker: Waters

Column: SHODEX GPC KF-601 (2 pieces), KF-602, KF-602.5, KF-603

Flow rate: 0.5ml/min.

Column temperature: 40℃

Solvent used: THF (tetrahydrofuran)

Detector: RI (parallel refraction detector)

ㆍHPLC (high-performance liquid chromatography) analysis

Column: Inertsil ODS-2

Flow rate: 1.0ml/min.

Column temperature: 40℃

Solvent used: Acetonitrile, water

Detector: Photodiode array (225nm)

ㆍDSC analysis

A maker: TA Instruments

Device: DSC2500

Temperature increase rate: 10℃/min

Measurement temperature range: 30℃ ~ 350℃

ㆍDMA

Maker: TA Instruments

Device: DMAQ800

Measurement Mode: Tensile

Temperature increase rate: 2℃/min.

Measurement temperature range: 25℃ ~ 350℃

Measurement frequency: 10Hz

The temperature at which the value of tanδ reached its maximum was set as Tg.

ㆍTd5 analysis

Manufacturer: Seiko Stru Co., Ltd.

Device: TG/DTA6200

Measurement temperature range: 30℃ ~ 580℃

Temperature increase rate: 10℃/min

ㆍTMA

Maker: TA Instruments

Device: TMAQ400

Measurement Mode: Tensile

Temperature increase rate: 2℃/min.

Measurement temperature range: 25℃ ~ 330℃

ㆍMechanical strength

Manufacturer: Shimadzu Works

Device: Autograph AGS-X

Tensile speed: 0.5mm/min

The test piece was placed so that its length was 5 cm, and tension was measured in the 180° direction at the above-mentioned test speed.

ㆍPeel strength test

Manufacturer: Shimadzu Works

Device: Autograph AGS-X

Peel test tensile speed: 50mm/min

A rough surface of an electrolytic copper foil with a thickness of 18 μm (CF-T4X-SV-18: manufactured by Fukuda Metal Foil Industry Co., Ltd.), and an electrolytic copper foil with a thickness of 35 μm (CF-T9B-HTE: manufactured by Fukuda Metal Foil Industry Co., Ltd.) A test piece was produced by sandwiching the curable resin composition with the rough surface of (manufactured) and curing it at 220°C for 2 hours at a pressure of 1 MPa. After cutting the obtained test piece into 2cm wide pieces, the electrolytic copper foil with a thickness of 18μm was cut and removed so that a width of 1cm remained. An electrolytic copper foil with a width of 1 cm and a thickness of 18 μm was stretched in a 90° direction at the above test speed and the peel strength was measured.

ㆍAbsorption rate test

After immersion in water for 24 hours, the weight was measured and calculated after extraction and leaving in an environment of 25°C and 30% for 24 hours.

ㆍDielectric constant test, dielectric loss tangent test

Manufacturer: AET Co., Ltd.

Device: 10GHz cavity resonator

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

[Synthesis Example 1]

Synthesis of aromatic amine resin (A-1)

Into a flask equipped with a thermometer, cooling tube, Dean-Stark azeotropic distillation trap, and stirrer, add 192 parts of aniline, 112 parts of toluene, 100 parts of 1,3-bis(2-hydroxy-2-propyl)benzene, and 21.5 parts of 35% hydrochloric acid. It was added dropwise over 10 minutes. The temperature of the system was raised to 160°C, and the reaction was carried out at the same temperature for 17 hours while water and toluene were distilled off. 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. After that, it was stirred at the same temperature for 2 hours and left to stand for 30 minutes. The separated lower aqueous layer was removed, and washing of the reaction solution was repeated until the washing solution became neutral. Next, excess aniline and toluene were distilled off from the oil layer under heating and reduced pressure using a rotary evaporator, thereby obtaining 158 parts of the aromatic amine resin (A-1) represented by the above formula (2). The amine equivalent weight of the aromatic amine resin (A-1) was 186.1 g/eq, and the softening point was 58.8°C. By GPC analysis (RI), n = 1 body was 62.5 area%. The GPC chart is depicted in Figure 1.

[Synthesis Example 2]

Synthesis of maleimide resin (M-1)

Add 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 into a flask equipped with a thermometer, cooling tube, Dean-Stark azeotropic distillation trap, and stirrer and heat. It was placed in a reflux state. Next, a resin solution in which 93 parts of aromatic amine resin (A-1) was dissolved in 55.8 parts of toluene was added dropwise over 4 hours while maintaining the reflux state. During this period, the condensed water and toluene, which were azeotropically released under reflux conditions, were cooled and separated in a Dean-Stark azeotropic distillation trap, and then the organic layer, toluene, was returned to the system and the water was discharged to the outside of the system. After completion of the dropwise addition of the resin solution, the reflux state was maintained and the reaction was performed for 10 hours while performing a dehydration operation.

After completion of the reaction, water washing was repeated four times to remove methanesulfonic acid and excess maleic anhydride, and water was removed from the system by azeotropic ratio of toluene and water under heating and reduced pressure at 70°C or lower. Next, 0.93 part of methanesulfonic acid was added, and reaction was performed for 4 hours under heating and reflux. After completion of the reaction, washing with water was repeated 4 times until the washing water became neutral, water was removed from the system by heating and reducing pressure at 70°C or lower by azeotropic ratio of toluene and water, and then toluene was heated to reduce pressure to about 70 - 80%. After distilling off the solvent until the resin concentration was reached, toluene was added to adjust the resin concentration to 60%. As a result, a maleimide solution (V-1) containing the maleimide (M-1) of the present invention was obtained. According to GPC analysis (RI), the n = 1 body of the obtained maleimide resin (M-1) was 57.4 area%, the n = 2 body was 21.3 area%, and the n = 3 or more bodies was 21.3 area%. The orientation ratio (ortho-ortho body/para-para body/ortho-para body) in n=1 body was 32.0%/25.4%/42.6% from HPLC analysis (225 nm). Additionally, the softening point was 115.5°C and the viscosity was 6.0 Pa·s. The GPC chart is depicted in Figure 2.

[Reference Example 1, Examples 2 to 5, Comparative Examples 1 to 6]

A varnish was produced by measuring the maleimide compound and the polyphenylene ether compound having an unsaturated double bond in the ratio shown in Table 1, adding toluene so that the resin solid content was 50%, and then heating and mixing at 70°C for 1 hour. The solubility and compatibility of the resin at this time were confirmed visually and evaluated under the conditions described later. The results are shown in Table 1.

Additionally, DCP (dicumyl peroxide, manufactured by Kayakunurion Co., Ltd.) was dissolved in the varnish as a curing accelerator. A curable resin composition was prepared by heating the varnish in which the curing accelerator was dissolved in 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 foil and 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. The results of various measurements on the obtained cured product are shown in Table 1.

Conditions for determining solubility: ○ㆍㆍㆍNo precipitation in solution

× ㆍㆍㆍPrecipitation in solution

Conditions for determining compatibility: ○ㆍㆍㆍCommercially used

×····Not in commercial use (phase separated)

Conditions for determining curability at 220℃: ○ㆍㆍㆍcured product obtained

: ×ㆍㆍㆍCannot obtain hardened product (hardened product is soft and cannot be taken out)

ㆍM-1 (the solvent obtained in Synthesis Example 2 was distilled off by heating and reducing pressure)

ㆍMIR-3000 (the solvent of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd.) was distilled off by heating and reduced pressure)

ㆍBMI-70 (manufactured by K-Aikasei Co., Ltd.)

ㆍBMI-2300 (manufactured by Daiwa Kasei Co., Ltd.)

ㆍSA-9000-111 (manufactured by Sabic) Mw: 3653, Mn: 2648

ㆍOPE-2st1200 (manufactured by Mitsubishi Gas Chemical Company) Mn: 1200

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

Claims (7)

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

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

(In formula (1), R represents a hydrogen atom or a methyl group. m represents an integer from 0 to 3. n is the number of repetitions, and the average value 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).
[Formula 3]

(In equation (2), n is the number of repetitions, and its average value is 1 < n < 10.)
[Formula 4]

(In equation (4), n is the number of repetitions, and its average value is 1 < n < 10.) The curable resin composition according to any one of claims 1 to 4, further comprising a curing accelerator. A prepreg comprising the curable resin composition according to any one of claims 1 to 5 on a sheet-shaped fiber substrate. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5, or the prepreg according to claim 6.