KR20240082262A - Amine compounds, maleimide compounds, curable resin compositions and their cured products - Google Patents

Abstract

The present invention provides a maleimide compound that exhibits excellent heat resistance and electrical properties and has good curability, a curable resin composition, and an amine compound serving as a raw material thereof. A maleimide compound represented by the following formula (1).
[Formula 1]

(In formula (1), plural R's each exist independently and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n is the number of repetitions, 0≤m<20, 1<n<20.)

Description

Amine compounds, maleimide compounds, curable resin compositions and their cured products

The present invention relates to an amine compound, a maleimide compound, a curable resin composition, and a cured product thereof having a specific structure, and is applicable to electrical and electronic components such as semiconductor encapsulation materials, printed wiring boards, and build-up laminates, carbon fiber reinforced plastic, and glass. It is preferably used for lightweight, high-strength materials such as fiber-reinforced plastics and 3D printing applications.

Recently, the required characteristics of laminated boards carrying electrical and electronic components have become wider and more sophisticated as their fields of use have expanded. Conventional semiconductor chips were mainly mounted on metal lead frames, but semiconductor chips with high processing capabilities, such as central processing units (hereinafter referred to as CPUs), are increasingly mounted on laminated boards made of polymer materials.

In particular, in semiconductor packages (hereinafter referred to as PKG) used in smartphones, etc., thinning of the PKG substrate is required to meet the demands for miniaturization, thinness, and high density. However, as the PKG substrate becomes thinner, the rigidity decreases, so PKG is used as the main device. Problems such as significant bending may occur due to heating when soldering on a board (PCB). To reduce this, PKG board materials with a high Tg above the solder mounting temperature are required.

In addition, the 5th generation communication system "5G", the development of which is currently accelerating, is expected to lead to new high-capacity and high-speed communication. In 5G, the frequencies used are becoming higher and higher, and the realization of high-speed communication using high frequencies requires further improvement in the performance of substrate materials. For example, it is important to have low dielectric properties to reduce transmission loss, and the dielectric loss tangent is required to be 0.005 or less at at least 10 GHz. Transmission loss occurring on a printed circuit board results from conductor loss and dielectric loss (Non-patent Document 1). Conductor loss is due to the resistance component of conductors such as wiring on a board, and is divided into loss due to surface effects at high frequencies and scattering loss due to the roughness of the copper foil surface. Since the higher the frequency, the closer the electrical signal flows to the surface of the copper foil (distance from the surface of the copper foil: 1 GHz: 2.1 μm, 10 GHz: 0.66 μm), in order to reduce the surface effect, the illuminance of the copper foil has recently been reduced. From this, one of the requirements for resin materials is ensuring adhesion to low-illuminance copper foil, but low-dielectric materials such as PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer) lack adhesion. Additionally, since these materials are thermoplastic materials, they lack formability. Considering this, there is a need for the development of thermosetting resins with excellent adhesion, low dielectric properties, and moldability.

In addition, as electronics progresses in the automotive field and precision electronic devices are sometimes placed near engine driving parts, higher levels of heat and moisture resistance are required. SiC semiconductors are beginning to be used in trains, air conditioners, etc., and since extremely high heat resistance is required for encapsulation materials for semiconductor devices, conventional epoxy resin encapsulation materials cannot cope with this.

Against this background, polymer materials that can achieve both heat resistance and low dielectric loss characteristics are being examined. For example, Patent Document 1 proposes a composition containing a maleimide resin and a phenol resin containing a propenyl group. However, on the other hand, the electrical properties cannot be said to be sufficient because phenolic hydroxyl groups that are not involved in the reaction remain during the curing reaction. Additionally, Patent Document 2 discloses an allyl ether resin in which a hydroxyl group is replaced with an allyl group. However, there are cases where Claisen dislocation occurs at 190°C, and at 200°C, which is the typical molding temperature for substrates, the electrical properties cannot be satisfied because phenolic hydroxyl groups that do not contribute to the curing reaction are generated.

[Patent Document 1] Japanese Patent Application Publication No. 04-359911 [Patent Document 2] International Publication No. 2016/002704

[Non-patent Document 1] Signal loss factors in high-speed signal transmission on printed boards (Mitsui Metal Mining Co., Ltd.) 29th Electronics Installation Society Spring Contest 16 P1-17

The present invention was made in view of this situation, and its purpose is to provide a maleimide compound that exhibits excellent heat resistance and electrical properties and has good curability, a curable resin composition, and an amine compound that serves as a raw material thereof.

As a result of intensive research to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to the following [1] to [7]. In addition, in this application, “(numerical value 1) to (numerical value 2)” indicates that the upper and lower limit values are included.

[One]

A maleimide compound represented by the following formula (1).

[Formula 1]

(In formula (1), plural R's each exist independently and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n is the number of repetitions, 0≤m<20, 1<n<20.)

[2]

A maleimide compound represented by the following formula (2).

[Formula 2]

(In equation (2), m and n are the number of repetitions, and 0≤m<20, 1<n<20.)

[3]

The maleimide compound according to the preceding item [1] or [2], which has a weight average molecular weight of 300 to 3000 as determined by gel permeation chromatography (GPC).

[4]

A curable resin composition containing the maleimide compound according to any one of the preceding items [1] to [3].

[5]

The curable resin composition according to the preceding paragraph [4], further containing a radical polymerization initiator.

[6]

A cured product obtained by curing the curable resin composition according to the preceding item [4] or [5].

[7]

An amine compound represented by the following formula (3).

[Formula 3]

(In formula (3), plural R's each exist independently and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n is the number of repetitions, 0≤m<20, 1<n<20.)

The maleimide compound of the present invention has excellent curability, and its cured product has excellent heat resistance and low dielectric properties. Therefore, it is a useful material for encapsulation of electrical and electronic components, circuit boards, and carbon fiber composite materials.

[Figure 1] Shows the GPC chart of Example 1.
[Figure 2] shows the GC-MS chart of Example 1.
[Figure 3] shows a chart of GPC of Example 2.
[Figure 4] shows the GC-MS chart of Example 2.
[Figure 5] shows the DSC chart of Example 3.
[Figure 6] shows the DSC chart of Comparative Example 1.

The maleimide compound of the present invention can be obtained by reacting maleic anhydride with an amine compound obtained by reacting aniline with a Prins reaction product obtained by reacting an aromatic vinyl compound and an aromatic aldehyde in the presence of a protonic acid catalyst.

The maleimide compound of the present invention is represented by the following formula (1).

[Formula 4]

(In formula (1), plural R's each exist independently and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n is the number of repetitions, 0≤m<20, 1<n<20.)

The compound represented by the above formula (1) has excellent heat resistance, high fluidity, and low dielectric properties due to its molecular design incorporating polystyrene segments.

In the above equation (1), the value of n can be calculated from the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) or the area ratio of each separated peak. The value of n is more preferably 1<n<15, and particularly preferably 1<n<10. In the above equation (1), the value of m can be calculated from the number average molecular weight obtained by measurement by gel permeation chromatography (GPC, detector: RI) or the area ratio of each separated peak. The value of m is more preferably 0≤m<15, and particularly preferably 0≤m<10.

The compound represented by the above formula (1) preferably has a weight average molecular weight of 300 to 3000, more preferably 350 to 2500, and still more preferably 400 to 2000, as measured by GPC. The weight average molecular weight as determined by GPC is preferably 200 to 3000, more preferably 250 to 2500, and still more preferably 300 to 2000.

When the weight average molecular weight and number average molecular weight are less than the lower limit of the above range, it is difficult to obtain the effect of improving heat resistance by increasing the molecular weight. In addition, when the weight average molecular weight and number average molecular weight are greater than the upper limit of the above range, purification by water washing, etc. becomes difficult, and when used as a semiconductor encapsulant, etc., the viscosity is too high and fluidity cannot be secured, making filling between wires difficult. Even for substrate use, it becomes difficult to secure the fluidity of the prepreg, which impairs the embedding properties of the wiring.

The compound represented by the above formula (1) is usually in the form of a solid resin at room temperature, and its softening point is preferably 180°C or lower, and more preferably 150°C or lower. If the softening point is higher than 180°C, the viscosity is high and the fiber impregnability decreases when preparing prepreg.

An example of a preferable structure of the compound represented by the above formula (1) includes the compound represented by the following formula (2). This is because by including various orientations, crystallinity is lowered, solvent solubility is expected to be improved, and a decrease in elastic modulus and heat resistance due to introduction of an alkyl group can be prevented.

[Formula 5]

(In equation (2), m and n are the number of repetitions, and 0≤m<20, 1<n<20.)

The preferable ranges of m and n in the above formula (2) are the same as those in the above formula (1).

The method for producing the maleimide compound of the present invention is not particularly limited, but involves reacting an aromatic vinyl compound and an aromatic aldehyde in the presence of a protonic acid catalyst to obtain a reactant, and then reacting aniline with an amine compound obtained by reacting maleic anhydride. You can get it.

More specifically, it can be obtained by reacting a styrene-based compound and a benzaldehyde-based compound under an acid catalyst such as sulfonic acid, adding an aniline-based compound, heating and reacting again, and reacting the obtained amine compound with maleanhydride.

A preferable structure as the amine compound is represented by the following formula (3).

[Formula 6]

(In formula (3), plural R's each exist independently and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n is the number of repetitions, 0≤m<20, 1<n<20.)

(In equation (3), m and n are the number of repetitions, and 0≤m<20, 1<n<20.)

The preferred ranges of R, m, n, p, and q in the formula (3) are the same as those in the formula (1).

The compound represented by the above formula (3) preferably has a weight average molecular weight of 200 to 3000, more preferably 250 to 2500, and even more preferably 300 to 2000, as measured by GPC. The weight average molecular weight as determined by GPC is preferably 150 to 3000, more preferably 200 to 2500, and still more preferably 250 to 2000.

When the weight average molecular weight and the number average molecular weight are less than the lower limit of the above range, it is difficult to obtain the effect of improving heat resistance by increasing the molecular weight when a cured product is prepared using a derivative such as maleimide derived from formula (3) or the amine compound itself. Additionally, when the weight average molecular weight and number average molecular weight are greater than the upper limit of the above range, purification by washing with water, etc. becomes difficult.

Here, the manufacturing method of the amine compound represented by the above formula (3) will be described. The method for producing the amine compound represented by the above formula (3) is not particularly limited, but for example, a styrene-based compound and a benzaldehyde-based compound are subjected to a prince reaction in the presence of an acid catalyst such as sulfonic acid, then an aniline-based compound is added and heated again. ·Can be obtained by reacting. At this time, the substituent of the aniline-based compound is preferably unsubstituted or has an alkyl group having 1 to 5 carbon atoms, and from the viewpoint of improving heat resistance, it is more preferable to be unsubstituted or have an alkyl group having 1 to 3 carbon atoms. During synthesis, the acid catalysts are hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluene sulfonic acid, and methane sulfonic acid, as well as Lewis acids such as aluminum chloride and zinc chloride, and solid acids such as activated clay, acid clay, white carbon, zeolite, and silica alumina. , acidic ion exchange resin, etc. can be used. These may be used alone or in combination of two or more. The amount of catalyst used is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the styrene-based compound and benzaldehyde-based compound, which are reaction substrates. If the amount of catalyst used is too large, there is a risk of increasing unnecessary waste, and if the amount of catalyst used is too small, there is a risk of slowing down the progress of the reaction. Solvents to be used include, 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, Non-aqueous solvents include, but are not limited to, ketone-based solvents such as methyl isobutyl ketone and cyclopentanone, and two or more types may be used in combination. Additionally, in addition to the above-mentioned non-aqueous solvent, an aprotic polar solvent can also be used together. Examples include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. Two or more types may be used in combination. . When using a non-protonic polar solvent, it is preferable to use one with a higher boiling point than the non-aqueous solvent used together. The reaction temperature is preferably 80 to 250°C, more preferably 90 to 240°C, and even more preferably 100 to 230°C. If the reaction temperature is too high, there is a risk that the Prince reaction product (in this specification, a styrene-based compound and a benzaldehyde-based compound reacted with an acid catalyst) may volatilize, and if the reaction temperature is too low, there is a risk that the reaction may not proceed sufficiently. Since water is produced as a by-product during the reaction between the Prince reaction product and the phenol-based compound, it is removed from the system while azeotroping with the solvent when the temperature is raised. After completion of the reaction, the acidic catalyst is neutralized with an aqueous alkaline solution, etc., a non-water-soluble organic solvent is added to the oil layer, and washing with water is repeated until the waste water becomes neutral, and then the solvent is 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.

The reaction conditions for maleimidation are not particularly limited, but examples of solvents used include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, and ethers such as diethyl ether and diisopropyl ether. Insoluble solvents include, but are not limited to, ester-based solvents such as ethyl acetate and butyl acetate, and ketone-based solvents such as methyl isobutyl ketone and cyclopentanone, and two or more types may be used in combination. Additionally, in addition to the above-mentioned water-insoluble solvent, an aprotic polar solvent can also be used together. Examples include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone, etc. Two or more types may be used in combination. . When using an aprotic polar solvent, it is preferable to use one with a higher boiling point than the non-aqueous solvent used together. During the reaction, as needed, catalysts include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluene sulfonic acid, and methane sulfonic acid, as well as Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, silica alumina, etc. Solid acids, acidic ion exchange resins, etc. can be used. These may be used alone or in combination of two or more. The amount of catalyst used is usually 0.1 to 0.8 mol, preferably 0.2 to 0.7 mol, per mole of amino group of the amine compound used. If the amount of catalyst used is too large, the viscosity of the reaction solution may be too high, making stirring difficult, and if it is too small, the progress of the reaction may be slowed down. Additionally, as a cocatalyst for imidization, a basic cocatalyst such as triethylamine can be used alone or in combination. When a sulfonic acid or the like is used as a catalyst, the extraction step may be performed after neutralization with an alkali metal such as sodium hydroxide or potassium hydroxide. For the extraction step, an aromatic hydrocarbon solvent such as toluene or xylene may be used alone, or a non-aromatic hydrocarbon solvent such as cyclohexane or toluene may be used in combination. After extraction, the organic layer is washed with water until the drainage water becomes neutral, and the solvent is removed using an evaporator or the like to obtain the target maleimide compound.

The amine compound represented by the above formula (3) is more preferably represented by the following formula (4).

[Formula 7]

(In equation (4), m and n are the number of repetitions, and 0≤m<20, 1<n<20.)

The preferable ranges of m and n in the above formula (4) are the same as those in the above formula (3).

The curable composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, storage stability is improved and the reaction start temperature can be controlled. By controlling the reaction start temperature, it becomes easy to secure fluidity, so that the impregnability for glass cloth, etc. is not impaired, and B-stage conversion such as prepreg becomes easy. If the polymerization reaction proceeds excessively during prepreg, problems such as difficulty in lamination are likely to occur in the lamination process.

Polymerization inhibitors that can be used include polymerization inhibitors such as phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitrone-based, and nitroxyl radical-based agents. The polymerization inhibitor may be added when synthesizing the maleimide compound of the present invention, or may be added after synthesis. Moreover, the polymerization inhibitor can be used individually or in combination of two or more types. The amount of the polymerization inhibitor used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the resin component. These polymerization inhibitors can be used individually, but two or more types may be used in combination. In the present invention, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based are preferred.

Specific examples of phenolic polymerization inhibitors include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and stearyl-β-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4- Bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl ] Monophenols such as -o-cresol; 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3- Methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl) -4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'- Hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydride) Roxyphenyl) propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2-{β-(3) -t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl Bisphenols such as calcium (ethyl)4-hydroxybenzylsulfonate); 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t- Butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3' -bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid] glycol ester, tris(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3 Polymers such as ,5-tris(3', 5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2, 4, 6-(1H, 3H, 5H)trione, tocopherol, etc. Type phenols are exemplified.

Specific examples of sulfur-based polymerization inhibitors include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate. Nate et al. are examples.

Specific examples of phosphorus-based polymerization inhibitors include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, and tris (2,4-di- t-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis( 2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogenphosphite Phosphites such as; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9 -Oxaphosphaphenanthrene oxides such as oxa-10-phosphaphenanthrene-10-oxide and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide. etc. are exemplified.

Specific examples of hindered amine-based polymerization inhibitors include Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Dekastab LA-82, and Dekastabe LA-. 81, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-72, Adekastab LA-68, Adekastab LA-63P, Adekastab LA-57, Adekastab LA-52 , Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, TinuvinPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, Tinuvin791FB, etc., but are not limited thereto.

Specific examples of nitroso-based polymerization inhibitors include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxyamine, (cuperone), etc., preferably N-nitrosophenyl. It is the ammonium salt (cuperone) of hydroxyamine.

Specific examples of nitroxyl radical polymerization inhibitors include di-tert-butylnitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-hydroxy-2,2,6,6- Tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine- 1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, etc. are mentioned, but are not limited to these.

The curable resin composition of the present invention is a curable resin other than the maleimide compound of the present invention, and any known material can be used. Specifically, phenol resin, epoxy resin, amine resin, activated alkene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, propenyl resin, metaryl resin, activated ester resin, etc. You may use one type or multiple types together. Additionally, it is preferable to contain an epoxy resin, an activated alkene-containing resin, or a cyanate ester resin to balance heat resistance, adhesion, and dielectric properties. By containing such a curable resin, the friability of the cured product can be improved and adhesion to metal can be improved, and cracks in the package can be suppressed in reliability tests such as solder reflow or cooling/heating cycles.

The amount of the curable resin used is preferably 10 mass times or less, more preferably 5 mass times or less, and particularly preferably 3 mass times or less, relative to the maleimide compound of the present invention. Moreover, the preferable lower limit is 0.5 mass times or more, more preferably 1 mass times or more. If it is 10 times by mass or less, the effects of heat resistance and dielectric properties of the maleimide compound of the present invention can be utilized.

As phenol resin, epoxy resin, amine resin, activated alkene-containing resin, isocyanate resin, polyamide resin, polyimide resin, cyanate ester resin, and activated ester resin, those exemplified below can be used.

Phenol resin: Phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcin, naphthol, alkyl-substituted naphthol, dihydroxy benzene, alkyl-substituted dihydroxy benzene, dihydroxy naphthalene, etc.) and various aldehydes (formum) Polycondensates with aldehydes, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), phenols and various diene compounds (DC) Polymers with chlorpentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) , 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 (1,4-bis(chloromethyl) benzene, 1,4-bis(methoxymethyl) ) Phenol resins obtained by polycondensation with benzene and 1,4-bis(hydroxymethyl) benzene, etc., polycondensates of bisphenols and various aldehydes, and polyphenylene ether compounds.

Any known polyphenylene ether compound may be used, but from the viewpoint of heat resistance and electrical properties, it is preferable that it is a polyphenylene ether compound with an ethylenically unsaturated double bond, and a polyphenylene ether compound with an acrylic group, methacryl group, or styrene structure. It is more preferable that it is a polyphenylene ether compound. Commercially available products include SA-9000-111 (manufactured by SABIC, a polyphenylene ether compound with a methacryl group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound with a styrene structure).

The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the molecular weight is less than 500, sufficient heat resistance of the cured product tends not to be obtained. Additionally, if the molecular weight is greater than 5000, the melt viscosity increases and sufficient fluidity cannot be obtained, which tends to result in molding defects. In addition, the reactivity is lowered, so a long time is required for the curing reaction, and the amount of unreacted material that is not accepted into the curing system increases, which tends to lower the glass transition temperature of the cured product and lower the heat resistance of the cured product.

If the polyphenylene ether compound has a number average molecular weight of 500 to 5000, excellent heat resistance and moldability can be achieved while maintaining excellent dielectric properties. In addition, the number average molecular weight here can be specifically measured using gel permeation chromatography or the like.

The polyphenylene ether compound may be obtained through a polymerization reaction or may be obtained through a redistribution reaction of a high molecular weight polyphenylene ether compound with a number average molecular weight of about 10,000 to 30,000. Additionally, radical polymerization may be imparted by using these as raw materials and reacting them with a compound having an ethylenically unsaturated double bond, such as methacryl chloride, acrylic chloride, or chloromethylstyrene. The polyphenylene ether compound obtained by the redistribution reaction can be obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a radical initiator and performing a redistribution reaction. In this way, the polyphenylene ether compound obtained through the redistribution reaction not only maintains higher heat resistance because it has hydroxyl groups derived from phenolic compounds that contribute to hardening at both ends of the molecular chain, but also has an ethylenically unsaturated double bond. It is preferable in that functional groups can be introduced into both ends of the molecular chain even after modification with a compound. 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 a polyphenylene ether compound obtained through a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, it can be considered to adjust the amount of the phenolic compound used in the redistribution reaction. In other words, the larger the amount of the phenol-based compound, the lower the molecular weight of the polyphenylene ether compound obtained. At this time, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as a high molecular weight polyphenylene ether compound that undergoes a redistribution reaction. 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 novolac, etc. This is preferably used. These may be used individually or in combination of two or more types.

The content of the polyphenylene ether compound is not particularly limited, but is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the curable resin components. If the content of the polyphenylene ether compound is 10 to 90% by mass, it is preferable to obtain a cured product that not only has excellent heat resistance, but also fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

Epoxy resin: Glycidyl ether-based epoxy resin obtained by glycidylating the above phenol resins, alcohols, etc., 4-vinyl-1-cyclohexenediepoxide or 3,4-epoxycyclohexylmethyl-3, 4'-epoxycyclo. Alicyclic epoxy resins, such as hexane carboxylate, glycidylamine-based epoxy resins, such as tetraglycidyldiaminodiphenylmethane (TGDDM) and triglycidyl p-aminophenol, and glycidyl esters. Based epoxy resin.

Amine resin: diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolak, orthoethylaniline novolak, aniline resin obtained by reaction of aniline with xylene chloride, patented in Japan. Aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl described in Publication No. 6429862 etc.), or can be obtained by reaction with substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1,4-bis(hydroxymethyl)benzene, etc.) Aniline resin.

Active alkene-containing resin: polycondensate of the above phenol resin and halogen-based compounds containing active alkene (chloromethylstyrene, allyl chloride, metalyl 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, 1,4- Polycondensate of bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), epoxy resin or Polycondensates of alcohols and substituted or unsubstituted acrylates (acrylates, methacrylates, etc.), maleimide resins (4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebis) Maleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5, 5'-diethyl-4,4'-diphenylmethanebismaleimide , 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimide phenoc Si) Benzene, 1,3-bis(4-maleimidephenoxy)benzene), ZYLOCK type maleimide resin (Anilix maleimide, manufactured by Mitsui Chemical Fine Co., Ltd.), biphenyl aralkyl type maleimide Resin (solidified by distilling off the solvent under reduced pressure a resin solution containing the maleimide resin (M2) described in Example 4 of Japanese Patent Application Laid-open No. 2009-001783) Bisaminocumylbenzene type maleimide (International Publication No. 2020/ maleimide resin described in No. 054601).

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; A polyisocyanate that can be obtained by urethanization reaction between the above isocyanate compound and a polyol compound.

Polyamide resin: amino acids (6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethyl benzoic acid, etc.), lactams (ε-caprolactam, ω-undecanactam, ω-laurolactam) ) and diamines (ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, Tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-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 xylenediamine; 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, 2-chloroterephthalic acid, 2 -Aromatic dicarboxylic acids such as methyl terephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; A polymer containing at least one selected from a mixture of dialkyl esters and dichlorides as the main raw material.

Polyimide resin: the above diamine 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-benzenetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-di Phenylsulfonetetracarboxylic 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, 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-dicarboxy) Phenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1, 2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracetetracarboxylic dianhydride, 1,2,7, 8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride), cyclo Pentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4' -Bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Levonic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane- 1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-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]octo-7-ene2,3,5,6-tetracarboxylic acid dianhydride, rel-[1S,5R,6R]-3-oxa Bicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran -3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl)ether, 4,4'- Biphenylbis(trimellitic monoester acid anhydride), polycondensation product with 9,9'-bis(3,4-dicarboxyphenyl) fluorene dianhydride).

Cyanate ester resin: A cyanate ester compound that can be 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 ester 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, and lead acetylacetonate. , dibutyl tin maleate, etc. may 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 other than the maleimide compound of the present invention, such as epoxy resin. 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 at least one of a carboxylic acid compound, 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 phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolnaphthaline, 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, tri. Hydroxybenzophenone, tetrahydroxybenzophenone, fluoroglycine, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, “dicyclopentadiene-type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester curing agent include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylate of phenol novolac, and benzoylates of phenol novolak. Active ester compounds can be mentioned. 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); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac; Active ester compounds containing benzoylates of phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation); “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester-based curing agent that is an acetylated product of phenol novolak; “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 improved by combined use of a curing accelerator (curing catalyst). 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 an olefin compound or maleimide compound or radical polymerization with other components. Radical polymerization initiators that can be used include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dicumyl peroxide, and 1,3-bis-(t-butyl peroxide). Dialkyl peroxides such as isopropyl)-benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, and α-cumyl peroxyneodecanoate. , t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexa Noate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, Alkyl peresters such as t-amyl peroxybenzoate, di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyisopropyl carbonate, 1,6 -Peroxycarbonates such as bis(t-butylperoxycarbonyloxy)hexane, and organic substances such as t-butylhydroperoxide, cumene hydroperoxide, t-butylperoxyoctoate, and lauroyl peroxide. Known curing of azo compounds such as peroxide, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile) Although accelerators may be mentioned, they are 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 addition amount of the radical polymerization initiator is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the curable resin composition. If the amount of radical polymerization initiator used is large, the molecular weight is not sufficiently expanded during the polymerization reaction.

Additionally, if necessary, a curing accelerator other than the radical polymerization initiator may be added or used in combination. 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 hexadecyltrimethylammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, and tetrabutylphosphonium salts (the counter ions of quaternary salts are halogen, Organic acid ion, hydroxide ion, etc. are not specifically designated, but organic acid ion and hydroxide ion are especially preferable.), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristic acid). and transition metal compounds (transition metal salts) such as zinc compounds such as zinc phosphate (octyl zinc phosphate, zinc stearyl phosphate, etc.). The mixing amount of the curing accelerator is 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

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 (dicylene phosphate). phosphoric acid esters such as xylenyl 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; Examples include phosphorus-containing epoxy compounds, red phosphorus, etc., which can be obtained by reacting epoxy resins with the active hydrogen of the phosphanes, but phosphoric acid esters, phosphenes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis ( Dixylenyl phosphate), 1,4-phenylenebis(dicxylenyl phosphate), 4,4'-biphenyl (dixylenyl phosphate) or phosphorus containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably in the range of (phosphorus-containing compound)/(total epoxy resin) (weight ratio) of 0.1 to 0.6. 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, hindered amine-based light stabilizers, especially HALS, are 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)butyl amine, 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-octyloxy) -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) etc. may be used alone, or two or more types may be used in combination.

Furthermore, 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 with respect to 100 parts by mass of the resin component, and more preferably 0.05 to 20 parts by mass.

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, and polyester. Powders such as light, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, and glass powder, or inorganic fillers made of these in spherical or crushed form can be added. Moreover, especially when obtaining a curable resin composition for semiconductor encapsulation, 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.

Known additives can be blended with 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 copolymers, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, silicone gel, silicone oil, and fillers such as silane coupling agents. surface treatment agents, mold release agents, and coloring agents 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, with respect to 100 parts by mass of the curable resin composition. From the viewpoint of low water absorption and electrical properties, polybutadiene and its modified products, polyphenylene ether, polystyrene, polyethylene, fluororesin, etc. are preferred. Polybutadiene and its modified products are preferred from the viewpoints of electrical properties, adhesion, and low water absorption. Specifically, butadiene-based thermoplastic elastomers such as styrene butadiene copolymer (SBR: RICON-100, RICON-181, RICON-184 all manufactured by Cray Valley, etc.) and acrylonitrile butadiene copolymer; styrene butadiene styrene copolymer. (SBS), hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer (SIS), hydrogenated styrene-isoprene-styrene copolymer, hydrogenated styrene (butadiene/isoprene) styrene copolymer, and other styrene-based thermoplastic elastomers. there is. These styrene-based thermoplastic elastomers may be used individually or two or more types may be used in combination. Among these high molecular weight materials, there are styrene-based thermoplastic elastomers such as styrene butadiene styrene copolymer, hydrogenated styrene butadiene styrene copolymer, styrene isoprene styrene copolymer, hydrogenated styrene isoprene styrene copolymer, and hydrogenated styrene (butadiene/isoprene) styrene copolymer. Preferred, in particular, styrene isoprene styrene copolymer, hydrogenated styrene butadiene styrene copolymer, hydrogenated styrene isoprene styrene copolymer, and hydrogenated styrene (butadiene/isoprene) styrene copolymer have higher heat resistance and are less prone to oxidation degradation. It is more desirable. Specifically, Septon 1020, Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, Septon 8004, 8006, Septon 8007L, Septon HG252 , Septon V9827, Hybra 7125 (hydrogenated), Hybra 7215F, Hybra 7311F (all manufactured by Kuraray Co., Ltd.). The weight average molecular weight of the styrene-based thermoplastic elastomer is not particularly limited as long as it is 10000 or more, but if it is too large, polyphenylene Other than ether compounds, compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability, so it is preferable that it is about 10,000 to 300,000. do. Generally, in the case of compounds containing heteroatoms such as oxygen or nitrogen, such as bismaleimide or polymaleimide, due to their polarity, among the additives or the curable resin components, compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons and It is difficult to ensure compatibility with the same low polarity compound. On the other hand, the maleimide compound having a polystyrene structure in the molecule described in the present invention has low polarity and low dielectric properties due to the fact that it is not a skeletal design that actively introduces heteroatoms such as oxygen or nitrogen (less polar groups). It has excellent compatibility with other materials or compounds composed only of hydrocarbons.

The curable resin composition of the present invention can be obtained by uniformly mixing the above components at a predetermined ratio, and is usually pre-cured at 130 to 180°C for 30 to 500 seconds, and further post-cured at 150 to 200°C for 2 to 15 hours. As a result, sufficient curing reaction can proceed and the cured product of the present invention can be 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 is useful as a material for all electrical and electronic components such as insulating materials, laminated boards (printed wiring boards, BGA substrates, build-up substrates, etc.), encapsulation 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. In particular, solder reflow resistance is beneficial in semiconductor encapsulation.

A semiconductor device has been encapsulated 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), TSOP (thin small outline package), and TQFP. (Thin quad flat package), etc.

The preparation method of the curable resin composition of the present invention is not particularly limited, but each component may be mixed uniformly or may be prepolymerized. For example, the maleimide compound of the present invention is prepolymerized by heating in the presence or absence of a catalyst and in the presence or absence of a solvent. Similarly, in addition to the maleimide compound of the present invention, 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, roller, etc. is used in the absence of a solvent, and a reaction pot equipped with a stirring device is used in the presence of a solvent.

As a method of uniformly mixing, kneading is performed using a device such as a kneader, roller, or planetary mixer at a temperature within the range of 50 to 100°C to obtain a uniform resin composition. The obtained 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-like molded body, or these compositions are melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm. It can also be used as a molded article of a curable resin composition. 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 one week.

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

An organic solvent can be added to the curable resin composition of the present invention to form a varnish-type composition (hereinafter 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. Additionally, if it is a liquid composition, a curable resin product 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-type composition. Specifically, it can be used to improve flexibility in the B-stage. Such a film-like 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 onto 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 is heated and melted to reduce viscosity, and a prepreg can be obtained by impregnating reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers. Specific examples include glass fibers such as E glasscloth, D glasscloth, S glasscloth, Q glasscloth, spherical glasscloth, NE glasscloth, and T glasscloth, as well as inorganic fibers other than glass and polyparaphenylene. 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 thereto. The shape of the base material is not particularly limited, but examples include woven fabric, non-woven fabric, roving, and chopped strand mat. Also, plain weave, basket weave, twill weave, etc. are known as methods for weaving woven fabrics, and these known methods can be appropriately selected and used depending on the intended use or performance. In addition, woven fabric that has been opened or 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 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 metal foil laminated board 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 by press molding, autoclave molding, sheet winding molding, etc., thereby heating and curing the electrical and electronic laminate ( 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 applications such as encapsulants for semiconductor devices, encapsulants for liquid crystal display devices, encapsulants for organic EL devices, printed wiring boards, and build-up laminates. ·It is preferably used in composite materials for lightweight, high-strength structural materials such as electronic components, carbon fiber reinforced plastic, and glass fiber reinforced plastic.

[Example]

Next, the present invention will be described in more detail by examples. Hereinafter, unless otherwise specified, parts are parts by mass. Additionally, the present invention is not limited to these examples.

Below, various analysis methods used in the examples are described.

<Gel permeation chromatography (GPC)>

The weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated by conversion to polystyrene using a polystyrene standard solution.

GPC: DGU-20A3R, LC-20AD, SIL-20AHT, RID-20A, SPD-20A, CTO-20A, CBM-20A (all manufactured by Shimadzu Corporation)

Column: Shodex KF-603, KF-602 x2, KF-601 x2)

Linking eluent: tetrahydrofuran

Flow rate: 0.5 ml/min

Column temperature: 40℃

Detection: RI (differential refraction detector)

·GC-MS (gas chromatography mass spectrometry) analysis

Device: JMS-Q1500GC made by JEOL

Column: Agilent HP-5ms 30 m×0.25 mm i.d. (film thickness 0.25 μm)

Carrier: He 1.5 mL/min Split 1/30

Injection temperature: 300℃

Oven temperature: 100℃(2 min)-310℃(37 min), increase temperature at 10℃/min

Ionization current: 70 eV

Ionization: EI

Sample injection: 1 μL

<Resin property measurement conditions>

·Amine equivalent weight

Measurement was made without using perchloric acid, referring to the method described in JIS K-7236, and the obtained value was taken as the amine equivalent. The unit is g/eq.

·Yeonhwa Branch

Measured using a method based on JISK-7234, the unit is ℃.

·ICI viscosity

It is measured by a method based on JISK-7117-2, and the unit is Pa·s.

[Example 1]

While purging nitrogen into a flask equipped with a thermometer, cooling tube, flow distribution tube, and stirrer, 100 parts of toluene, 26.0 parts of styrene (manufactured by Tokyo Chemical Company), and 26.5 parts of benzaldehyde (manufactured by Tokyo Chemical Company) were added, and p-toluene was added. 3.3 parts of sulfonic acid were added and reacted at 120°C for 4 hours. After cooling to room temperature, 93.1 parts of aniline and 26.1 parts of 35% hydrochloric acid were added, the water generated by dehydration was extracted along with toluene, the internal temperature was raised to 180°C, and reaction was carried out for 14 hours. After cooling to room temperature, the extracted toluene and water were returned to the system and neutralized by adding 39.2 parts of 30% sodium hydroxide aqueous solution. Thereafter, the organic layer was washed with water until the wastewater became neutral and concentrated to obtain 61.5 parts of amine compound (A1). The amine equivalent weight of amine compound (A1) was 325.9 g/eq, softening point was 80.9°C, and ICI viscosity (150°C) was 0.08 Pa·s. A chart when GPC analysis (RI) was performed is shown in Figure 1. The number average molecular weight (Mn) by GPC analysis was 410 and the weight average molecular weight (Mw) was 521. The GC-MS chart of the target compound is shown in Figure 2. From GC-MS analysis, it was confirmed that the amine compound represented by the above formula (3) was produced.

[Example 2]

100 parts of toluene, 25.0 parts of maleic anhydride, and 2.8 parts of methanesulfonic acid were added to a flask equipped with a thermometer, cooling tube, and stirrer, and heated and stirred until refluxed. A separately prepared amine solution (amine compound A1 synthesized in Example 1: 55.5 parts, toluene: 55.5 parts, NMP: 11.0 parts) was added dropwise under reflux and reacted under reflux for 2 hours. After cooling, the organic layer was washed 4 times with 100 parts of water, the organic layer was returned to the reaction vessel, 2.8 parts of methanesulfonic acid was added again, and the reaction was allowed to proceed for 2 hours under reflux. 150 parts of toluene was added, the organic layer was washed 5 times with 100 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain the target maleimide compound (M-1) as a brown solid resin. The GPC chart of the obtained maleimide compound is shown in Figure 3. The number average molecular weight (Mn) by GPC analysis was 602, and the weight average molecular weight (Mw) was 928. The GC-MS chart of the target maleimide compound is shown in Figure 4. From the GC-MS analysis, the number average molecular weight (Mn) by GPC analysis represented by the above formula (1) was 410, and the weight average molecular weight (Mw) was 521. It was confirmed that a compound was produced.

[Example 3, Comparative Example 1]

Each material was dissolved and blended in acetone in the ratio shown in Table 1 to a solid content of 50% by mass, preliminarily dried in a vacuum oven at 60°C for 30 minutes, and then dried at 150°C for 1 hour to obtain a powdery resin composition. After that, the 5G sample was vacuum pressed while sandwiching it with mirror-surface copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.) and cured at 220°C for 2 hours (for Comparative Example 1, it was cured at 175°C for 2 hours). At this time, a cushion paper with a thickness of 250 μm cut out in the center to 150 mm in length and width was used as a spacer. During the evaluation, the test piece was cut to the desired size using a laser cutter and evaluated as necessary.

<Dielectric constant test/dielectric loss tangent test>

Tests were conducted using the cavity resonator perturbation method using a 10 GHz cavity resonator manufactured by ATE Co., Ltd. The sample size was 1.7 mm in width x 100 mm in length, and the test was conducted with a thickness of 0.3 mm.

<Heat resistance (DSC)>

Differential scanning calorimeter: DSC6220 (manufactured by SI Nano Technology Co., Ltd.)

Measurement temperature range: 30 ~ 330℃

Temperature increase rate: 10℃/min

Atmosphere: Nitrogen (30 mL/min)

Sample amount: 5mg

Tg: The inflection point of the DSC chart was set to Tg.

The DSC charts of Example 3 and Comparative Example 1 are shown in Figures 5 and 6, respectively.

Example 3 Comparative Example 1 maleimide compounds M-1 100 epoxy resin NC-3000L 100 radical polymerization initiator DCP 1.0 Imidazole 2E4MZ 1.0 Evaluation results Tg(DSC) ℃ 246 147 Dielectric constant (10GHz) 2.6 2.9 dielectric loss tangent 0.0022 0.019

・NC-3000-L: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Explosives Co., Ltd.)

·DCP: Dicumyl peroxide (manufactured by Tokyo Kasei Corporation)

・2E4MZ: 2-ethyl-4-methylimidazole (curing accelerator, manufactured by Shikoku Chemical Company)

From the results in Table 1, it was confirmed that Example 3 had high heat resistance and low dielectric properties.

The curable resin composition of the present invention and its cured product are used for insulating materials for electrical and electronic components (high-reliability semiconductor encapsulation materials, etc.), laminated boards (printed wiring boards, BGA substrates, build-up substrates, etc.), adhesives (conductive adhesives, etc.), and CFRP. It is useful for various applications including composite materials, paints, and 3D printing.

Claims (7)

A maleimide compound represented by the following formula (1).
[Formula 1]

(In formula (1), plural R's each exist independently and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n is the number of repetitions, 0≤m<20, 1<n<20.) A maleimide compound represented by the following formula (2).
[Formula 2]

(In equation (2), m and n are the number of repetitions, and 0≤m<20, 1<n<20.) The maleimide compound according to claim 1 or 2, wherein the maleimide compound has a weight average molecular weight of 300 to 3000 as determined by gel permeation chromatography (GPC). A curable resin composition containing the maleimide compound according to any one of claims 1 to 3. The curable resin composition according to claim 4, further comprising a radical polymerization initiator. A cured product obtained by curing the curable resin composition according to claim 4 or 5. An amine compound represented by the following formula (3).
[Formula 3]

(In formula (3), plural R's each exist independently and are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number from 0 to 5, and q represents a real number from 0 to 4. m and n is the number of repetitions, 0≤m<20, 1<n<20.)