JP7236794B1 - Amine compound, maleimide compound, curable resin composition and cured product thereof - Google Patents

Abstract

Kind Code: A1 The present invention provides a maleimide compound, a curable resin composition, which exhibits excellent heat resistance and electrical properties and has good curability, and an amine compound as a raw material thereof.
A maleimide compound represented by the following formula (1).

(In the formula (1), each of a plurality of R exists independently and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number of 0 to 5, and q represents a real number of 0 to 4. represents m and n are the number of repetitions, 0 ≤ m < 20, 1 < n < 20.)
[Selection drawing] Fig. 2

Description

TECHNICAL FIELD The present invention relates to an amine compound, a maleimide compound, a curable resin composition, and a cured product thereof having a specific structure. It is suitable for lightweight high-strength materials such as fiber reinforced plastics and glass fiber reinforced plastics, and for 3D printing applications.

In recent years, due to the expansion of the fields of application of laminates on which electrical and electronic parts are mounted, the required properties are becoming more extensive and sophisticated. Conventional semiconductor chips are mainly mounted on metal lead frames, but semiconductor chips with high processing power such as central processing units (hereinafter referred to as CPUs) are mounted on laminates made of polymer materials. It is being installed more and more often.

In particular, semiconductor packages (hereinafter referred to as PKG) used in smartphones and the like are required to be thinner in order to meet the demands for smaller, thinner, and higher density PKG substrates. As the PKG becomes thinner, its rigidity decreases, and problems such as large warping occur due to heating when the PKG is solder-mounted to the motherboard (PCB). In order to reduce this, a PKG substrate material with a high Tg above the solder mounting temperature is required.

In addition, in the 5th generation communication system "5G", which is currently being developed, it is expected that further increase in capacity and high-speed communication will progress. In 5G, higher frequencies will be used, and in order to realize high-speed communication using high frequencies, further improvement in the performance of substrate materials will be required. 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 least at 10 GHz. Transmission loss that occurs on a printed circuit board originates from conductor loss and dielectric loss (Non-Patent Document 1). Conductor loss is caused by the resistance component of conductors such as wiring on a substrate, and is divided into loss due to the skin effect at high frequencies and scattering loss due to the roughness of the copper foil surface. Since electric signals flow closer to the surface of the copper foil at higher frequencies (distance from the surface of the copper foil is 1 GHz: 2.1 μm, 10 GHz: 0.66 μm), the surface roughness of the copper foil has been reduced in recent years in order to reduce the skin effect. progressing. For this reason, securing adhesion to low-roughness copper foil has become an issue as one of the requirements for resin materials. Low dielectric materials are represented by PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer). In addition, since these materials are thermoplastic materials, their moldability is also poor. Based on this, the development of thermosetting resins with excellent adhesion, low dielectric properties, and moldability is desired.

Furthermore, in the automotive field, the use of electronics is progressing, and precision electronic equipment is sometimes placed near the engine driving part, so a higher level of heat resistance and moisture resistance is required. SiC semiconductors have begun to be used in trains, air conditioners, and the like, and the encapsulating material for semiconductor elements is required to have extremely high heat resistance.

In view of this background, polymer materials capable of achieving both heat resistance and low dielectric loss tangent properties have been investigated. For example, Patent Document 1 proposes a composition containing a maleimide resin and a propenyl group-containing phenolic resin. However, since phenolic hydroxyl groups that do not participate in the reaction remain during the curing reaction, it cannot be said that the electrical properties are sufficient. Patent Document 2 discloses an allyl ether resin in which hydroxyl groups are substituted with allyl groups. However, it has been shown that Claisen rearrangement occurs at 190°C, and at 200°C, which is a general substrate molding temperature, phenolic hydroxyl groups that do not contribute to the curing reaction are generated, so electrical properties cannot be satisfied. do not have.

Signal loss factors in high-speed signal transmission on printed circuit boards (Mitsui Kinzoku Mining Co., Ltd.) The 29th Electronics Packaging Society Spring Conference 16P1-17

JP-A-04-359911 WO2016/002704

The present invention has been made in view of such circumstances, and provides 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 for these compounds. intended to provide

The present inventors have completed the present invention as a result of intensive research to solve the above problems. That is, the present invention relates to the following [1] to [7]. In the present application, "(numerical value 1) to (numerical value 2)" indicate that upper and lower limits are included.
[1]
A maleimide compound represented by the following formula (1).

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

(In formula (2), m and n are the number of repetitions, and 0≦m<20 and 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 [1] to [3] above.
[5]
The curable resin composition according to [4] above, further comprising a radical polymerization initiator.
[6]
A cured product obtained by curing the curable resin composition according to [4] or [5] above.
[7]
An amine compound represented by the following formula (3).

(In the formula (3), each of a plurality of R exists independently and is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p represents a real number of 0 to 5, and q represents a real number of 0 to 4. represents m and n are 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 properties such as high heat resistance and low dielectric properties. Therefore, it is a useful material for sealing electrical and electronic parts, circuit boards, carbon fiber composite materials, and the like.

1 shows a GPC chart of Example 1. FIG. The GC-MS chart of Example 1 is shown. 1 shows a GPC chart of Example 2. FIG. The GC-MS chart of Example 2 is shown. 4 shows a DSC chart of Example 3. FIG. 4 shows a DSC chart of Comparative Example 1. FIG.

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

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

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

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

In the formula (1), the value of n can be calculated from the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) or from the area ratio of each separated peak. More preferably, the value of n is 1<n<15, and most preferably 1<n<10. In the above formula (1), the value of m can be calculated from the number average molecular weight determined by gel permeation chromatography (GPC, detector: RI) or from 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 formula (1) preferably has a weight average molecular weight of 300 to 3,000, more preferably 350 to 2,500, and still more preferably 400 to 2,000 as measured by GPC. The weight average molecular weight by GPC measurement is preferably 200-3000, more preferably 250-2500, still more preferably 300-2000.
When the weight-average molecular weight and number-average molecular weight are less than the lower limits of the above ranges, it is difficult to obtain the effect of improving heat resistance by increasing the molecular weight. If the weight-average molecular weight and number-average molecular weight are larger than the upper limits of the above ranges, purification by washing with water, etc. becomes difficult, and in addition, the viscosity is too high when used as a semiconductor encapsulant, making it impossible to ensure fluidity. In addition, it becomes difficult to secure the fluidity of the prepreg in the substrate application, and the embedding property of the wiring is impaired.

The compound represented by the formula (1) is generally in the form of a solid resin at room temperature, and preferably has a softening point of 180° C. or lower, more preferably 150° C. or lower. If the softening point is higher than 180° C., the viscosity is high and the fiber impregnation property is lowered during prepreg preparation.

An example of a preferable structure of the compound represented by the formula (1) is a compound represented by the following formula (2). This is because the inclusion of various orientations lowers the crystallinity, improves the solubility in solvents, and prevents the reduction in elastic modulus and heat resistance due to the introduction of alkyl groups.

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

Preferred ranges of m and n in the formula (2) are the same as in the formula (1).

The method for producing the maleimide compound of the present invention is not particularly limited, but an amine compound obtained by reacting an aromatic vinyl compound and an aromatic aldehyde in the presence of a protonic acid catalyst to obtain a reaction product, and then further reacting an aniline with Obtained by reacting with maleic anhydride.

More specifically, after subjecting a styrene compound and a benzaldehyde compound to a Prins reaction in the presence of an acid catalyst such as sulfonic acid, an aniline compound is added, and the amine compound obtained by heating and reacting again is converted into maleic anhydride. It can be obtained by reacting with

A preferred structure for the amine compound is represented by the following formula (3).

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

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

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

The compound represented by the formula (3) preferably has a weight average molecular weight of 200 to 3,000, more preferably 250 to 2,500, and still more preferably 300 to 2,000 as measured by GPC. The weight average molecular weight by GPC measurement is preferably 150-3000, more preferably 200-2500, still more preferably 250-2000.
When the weight-average molecular weight and number-average molecular weight are less than the lower limits of the above ranges, when a cured product is prepared as a derivative such as maleimide derived from formula (3) or the amine compound itself, the effect of improving heat resistance can be obtained by increasing the molecular weight. is difficult. Further, when the weight-average molecular weight and the number-average molecular weight are larger than the upper limits of the above ranges, purification by washing with water or the like becomes difficult.

Here, a method for producing the amine compound represented by the formula (3) will be described. The method for producing the amine compound represented by the above formula (3) is not particularly limited. It can be obtained by heating and reacting again. At this time, the substituent of the aniline compound is preferably unsubstituted or having an alkyl group having 1 to 5 carbon atoms, and from the viewpoint of improving heat resistance, unsubstituted or an alkyl group having 1 to 3 carbon atoms It is more preferable to have a group. In addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid as acid catalysts during synthesis, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, A solid acid such as silica alumina, an acidic ion exchange resin, or the like can be used. These may be used alone or in combination of two or more. The catalyst is used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the styrene compound and benzaldehyde compound as reaction substrates. If the amount of catalyst used is too large, useless waste may increase, and if it is too small, the progress of the reaction may be slowed down. Examples of solvents to be used include 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. Water-insoluble solvents such as ketone-based solvents such as ketones and cyclopentanone are included, but are not limited to these, and two or more kinds may be used in combination. An aprotic polar solvent can also be used in combination with the water-insoluble solvent. Examples thereof include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like, and two or more of them may be used in combination. When an aprotic polar solvent is used, it is preferable to use one having a boiling point higher than that of the water-insoluble solvent used in combination. The reaction temperature is preferably 80 to 250°C, more preferably 90 to 240°C, even more preferably 100 to 230°C. If the reaction temperature is too high, the Prince reaction product (in this specification, a product obtained by reacting a styrene-based compound and a benzaldehyde-based compound with an acid catalyst) may volatilize, and if the reaction temperature is too low, the reaction will proceed sufficiently. I'm afraid not. Since water is by-produced during the reaction between the Prince reaction product and the phenolic compound, it is removed from the system while being azeotroped with the solvent when the temperature is raised. After completion of the reaction, the acidic catalyst is neutralized with an alkaline aqueous solution or the like, and a non-water-soluble organic solvent is added to the oil layer, and washing is repeated until the wastewater becomes neutral, and then the solvent is removed under heating and reduced pressure. When activated clay or ion exchange resin is used, the reaction solution is filtered to remove the catalyst after completion of the reaction.

The reaction conditions for maleimidation are not particularly limited, but examples of solvents to be used include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, ethers such as diethyl ether and diisopropyl ether, and ethyl acetate. , ester solvents such as butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone. An aprotic polar solvent can also be used in combination with the water-insoluble solvent. Examples thereof include dimethylsulfone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylpyrrolidone and the like, and two or more of them may be used in combination. When an aprotic polar solvent is used, it is preferable to use one having a boiling point higher than that of the water-insoluble solvent used in combination. In the reaction, if necessary, catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, activated clay, acid clay, white carbon, zeolite, A solid acid such as silica alumina, an acidic ion exchange resin, or the like can be used. These may be used alone or in combination of two or more. The amount of the catalyst used is generally 0.1-0.8 mol, preferably 0.2-0.7 mol, per 1 mol of the amino group of the amine compound used. If the amount of the catalyst used is too large, the viscosity of the reaction solution may be too high and stirring may become difficult. Also, as a co-catalyst for imidization, a basic co-catalyst 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 the extraction, the organic layer is washed with water until the waste water becomes neutral, and the solvent is distilled off using an evaporator or the like to obtain the desired maleimide compound.

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

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

Preferred ranges of m and n in the formula (4) are the same as in the formula (3).

The curable composition of the invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability is improved and the reaction initiation temperature can be controlled. By controlling the reaction initiation temperature, fluidity can be easily ensured, the ability to impregnate glass cloth or the like is not impaired, and B-stage processing such as prepreg formation is facilitated. If the polymerization reaction proceeds too much during prepreg formation, problems such as difficulty in lamination are likely to occur in the lamination step.
Polymerization inhibitors that can be used include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based polymerization inhibitors. The polymerization inhibitor may be added when synthesizing the maleimide compound of the present invention, or after synthesis. Moreover, a polymerization inhibitor can be used individually or in combination of 2 or more types. The amount of polymerization inhibitor used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component. Each of these polymerization inhibitors can be used alone, but two or more of them may be used in combination. In the present invention, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based solvents 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, 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) -monophenols such as 6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,4-bis[(octylthio)methyl]-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-hydroxy -hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxy benzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4, Bisphenols such as 8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t-butyl-4-hydroxybenzylsulfonic acid ethyl) calcium; 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)-y Socyanurate, 1,3,5-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol Polymer type phenols such as are exemplified.

Specific examples of sulfur-based polymerization inhibitors include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and the like. be.

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

Specific examples of hindered amine-based polymerization inhibitors include Adekastave LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, and Adekastab LA. －７７Ｇ、アデカスタブＬＡ－７２、アデカスタブＬＡ－６８、アデカスタブＬＡ－６３Ｐ、アデカスタブＬＡ－５７、アデカスタブＬＡ－５２、Ｃｈｉｍａｓｓｏｒｂ２０２０ＦＤＬ、Ｃｈｉｍａｓｓｏｒｂ９４４ＦＤＬ、Ｃｈｉｍａｓｓｏｒｂ９４４ＬＤ、Ｔｉｎｕｖｉｎ６２２ＳＦ、ＴｉｎｕｖｉｎＰＡ１４４、Ｔｉｎｕｖｉｎ７６５、Ｔｉｎｕｖｉｎ７７０ＤＦ、ＴｉｎｕｖｉｎＸＴ５５ＦＢ、Ｔｉｎｕｖｉｎ１１１ＦＤＬ、Ｔｉｎｕｖｉｎ７８３ＦＤＬ、Ｔｉｎｕｖｉｎ７９１ＦＢ等are exemplified, but not limited to.

Specific examples of the nitroso-based polymerization inhibitor include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salts of N-nitrosophenylhydroxyamine, (cupferron), and the like, preferably ammonium of N-nitrosophenylhydroxyamine. It is salt (cupferon).

Specific examples of nitroxyl radical polymerization inhibitors include di-tert-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 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 and the like, but are not limited to these.

The curable resin composition of the present invention can use any known material as a curable resin other than the maleimide compound of the present invention. Specific examples include phenol resins, epoxy resins, amine resins, active alkene-containing resins, isocyanate resins, polyamide resins, polyimide resins, cyanate ester resins, propenyl resins, methallyl resins, active ester resins, and the like. may be used in combination. Moreover, it is preferable to contain an epoxy resin, an active alkene-containing resin, and a cyanate ester resin from the balance of heat resistance, adhesion, and dielectric properties. By containing these curable resins, the brittleness of the cured product can be improved, the adhesion to metal can be improved, and cracks in the package can be suppressed during reliability tests such as solder reflow and thermal cycling.
The amount of the curable resin used is preferably 10 times by mass or less, more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass, relative to the maleimide compound of the present invention. Also, the lower limit is preferably 0.5 times by mass or more, more preferably 1 time by mass or more. If it is 10 times by mass or less, the effect of the heat resistance and dielectric properties of the maleimide compound of the present invention can be utilized.

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

Phenolic resin: phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc.), phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.); Polycondensates, phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), or substituted Phenolic resins and bisphenols obtained by polycondensation with phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.) and various aldehyde polycondensates, polyphenylene ether compounds.

Any known polyphenylene ether compound may be used, but from the viewpoint of heat resistance and electrical properties, it is preferably a polyphenylene ether compound having an ethylenically unsaturated double bond. or a polyphenylene ether compound having a styrene structure is more preferred. Commercially available products include SA-9000-111 (polyphenylene ether compound having a methacryl group, manufactured by SABIC) and OPE-2St 1200 (polyphenylene ether compound having a styrene structure, manufactured by Mitsubishi Gas Chemical Co.).
The number average molecular weight (Mn) of the polyphenylene ether compound is preferably from 500 to 5,000, more preferably from 2,000 to 5,000, and even more preferably from 2,000 to 4,000. If the molecular weight is less than 500, there is a tendency that the heat resistance of the cured product is insufficient. On the other hand, when the molecular weight is more than 5000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, so that molding defects tend to occur. In addition, reactivity also decreases, the curing reaction takes a long time, unreacted substances increase without being incorporated into the curing system, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product decreases. tend to
If the polyphenylene ether compound has a number average molecular weight of 500 to 5000, excellent heat resistance and moldability can be exhibited while maintaining excellent dielectric properties. The number average molecular weight here can be specifically measured using gel permeation chromatography or the like.

The polyphenylene ether compound may be obtained by a polymerization reaction or may be obtained by a redistribution reaction of a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000. Radical polymerizability may also be imparted by reacting these raw materials with a compound having an ethylenically unsaturated double bond, such as methacryl chloride, acryl chloride, chloromethylstyrene, or the like. The polyphenylene ether compound obtained by the redistribution reaction is obtained, for example, by heating a high molecular weight polyphenylene ether compound portion in a solvent such as toluene in the presence of a phenol compound and a radical initiator to cause a redistribution reaction. The polyphenylene ether compound obtained by such a redistribution reaction has hydroxyl groups derived from a phenolic compound that contributes to curing at both ends of the molecular chain. It is preferable because functional groups can be introduced to both ends of the molecular chain even after modification with a compound having a polyunsaturated double bond. A polyphenylene ether compound obtained by a polymerization reaction is also preferable because it exhibits excellent fluidity.

Adjustment of the molecular weight of the polyphenylene ether compound can be carried out by adjusting the polymerization conditions and the like in the case of the polyphenylene ether compound obtained by the polymerization reaction. In the case of the polyphenylene ether compound obtained by the redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction. More specifically, it is conceivable to adjust the blending amount of the phenolic compound used in the redistribution reaction. That is, the larger the amount of the phenolic compound compounded, the lower the molecular weight of the obtained polyphenylene ether compound. At this time, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as the high-molecular-weight polyphenylene ether compound that undergoes the redistribution reaction. The phenolic compound used in the redistribution reaction is not particularly limited, but for example, polyfunctional phenols having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolak, cresol novolak, etc. compounds are preferably used. These may be used alone or in combination of two or more.

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. When the content of the polyphenylene ether compound is 10 to 90% by mass, not only is it excellent in heat resistance, etc., but it is also preferable in terms of obtaining a cured product that fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

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

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

Active alkene-containing resins: Polycondensates of the above phenol resins and active alkene-containing halogen compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, allyl chloride, etc.), active alkene-containing phenols (2- allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds (4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4 -Bis(chloromethyl)benzene, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.) polycondensates, epoxy resins or alcohols and substituted or non-substituted Polycondensates of substituted acrylates (acrylates, methacrylates, etc.), maleimide resins (4,4′-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2′-bis[4-(4- Maleimidophenoxy)phenyl]propane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4′-diphenyletherbismaleimide , 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene), Zyloc type maleimide resin (Anilix maleimide, Mitsui Chemicals Fine Co., Ltd.) biphenylaralkyl-type maleimide resin (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide resin (M2) described in Example 4 of JP-A-2009-001783) Bisaminoc Mylbenzene-type maleimide (maleimide resin described in WO 2020/054601).

Isocyanate resins: p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, etc. Aromatic diisocyanates; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate and other aliphatic or alicyclic diisocyanates; one or more types of isocyanate monomers or an isocyanate trimerized from the above diisocyanate compound; a polyisocyanate obtained by a 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-aminomethylbenzoic acid, etc.), lactams (ε-caprolactam, ω-undecanelactam, ω-laurolactam) and "diamine (ethylenediamine , trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine , heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane; cyclohexanediamine, bis-(4 -aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane and other alicyclic diamines; Aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid; terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; dialkyl esters of these dicarboxylic acids, and dichlorides). A polymer made from one or more of these as main raw materials.

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-benzenetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride , 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetra Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic acid 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 anhydride, 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-di Carboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-di Carboxyphenoxy)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-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-na phthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrene Tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic 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) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) 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]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane- 2,4-dione-6-spiro-3′-(tetrahydrofuran-2′,5′-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro naphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4′-biphenylbis(trimellitic acid monoester anhydride), 9,9 '-Bis(3,4-dicarboxyphenyl)fluorene dianhydride).

Cyanate ester resin: A cyanate ester compound obtained by reacting a phenolic resin with cyanogen halide. Specific examples include dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2, 2 '-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl -4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone , bis(4-cyanatophenyl) thioether, phenol novolak cyanate, and phenol/dicyclopentadiene cocondensate in which the hydroxyl group is converted to a cyanate group, but are not limited thereto.
In addition, cyanate ester compounds whose synthesis method is described in JP-A-2005-264154 are particularly preferable as cyanate ester compounds because they are excellent in low hygroscopicity, flame retardancy and dielectric properties.
In order to trimerize the cyanate group to form a sym-triazine ring, the cyanate ester resin may be zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octylate, tin octylate, Catalysts such as lead acetylacetonate, dibutyltin maleate, and the like can also be included. The catalyst is usually used in an amount of 0.0001 to 0.10 parts by weight, preferably 0.00015 to 0.0015 parts by weight, per 100 parts by weight of the total weight of the curable resin composition.

Active ester resin: A compound having one or more active ester groups in one molecule can be used as a curing agent for a curable resin other than the maleimide compound of the present invention, such as an epoxy resin, if necessary. Active ester curing agents include 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. preferable. The active ester curing agent is preferably obtained by a condensation reaction of at least one of a carboxylic acid compound and a thiocarboxylic acid compound and at least one of a hydroxy compound and a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and at least one of a phenol compound and a naphthol compound. agents are preferred.
Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.
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 acetylated phenol novolac, and a benzoylated phenol novolac. active ester compounds containing Among them, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. "Dicyclopentadiene-type diphenol structure" represents 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", "HPC- 8000H-65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC); "EXB9416-70BK" (manufactured by DIC) as an active ester compound containing a naphthalene structure; acetylated phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent; "EXB-9050L-62M" manufactured by DIC Corporation as a phosphorus atom-containing active ester curing agent;

The curable resin composition of the present invention can be used in combination with a curing accelerator (curing catalyst) to improve curability. As a specific example of the curing accelerator that can be used, it is preferable to use a radical polymerization initiator for the purpose of promoting self-polymerization of radically polymerizable curable resins such as olefin compounds and maleimide compounds and 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, 1,3-bis-(t-butylperoxy Isopropyl)-benzene and other dialkyl peroxides, t-butyl peroxybenzoate, 1,1-di-t-butylperoxycyclohexane and other peroxyketals, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t- Butyl peroxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-amylperoxy Alkyl peresters such as benzoate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, t-butylperoxyisopropylcarbonate, 1,6-bis(t-butylperoxydicarbonate) oxycarbonyloxy)hexane and other peroxycarbonates, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, lauroyl peroxide and other organic peroxides and azobisisobutyronitrile, 4 , 4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2,4-dimethylvaleronitrile) known curing accelerators of azo compounds such as, but particularly limited to these not a thing Ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, percarbonates, etc. are preferred, and dialkyl peroxides are more preferred. The amount of the radical polymerization initiator to be added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of the radical polymerization initiator used is too large, the molecular weight will not be sufficiently elongated during the polymerization reaction.

In addition, if necessary, a curing accelerator other than the radical polymerization initiator may be added or used together. 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-diaza-bicyclo ( 5,4,0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl Quaternary ammonium salts such as ammonium hydroxide, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, quaternary phosphonium salts such as tetrabutylphosphonium salts (counter ions of the quaternary salts are halogen, Organic acid ions, hydroxide ions, etc. are not particularly specified, but organic acid ions and hydroxide ions are particularly preferred.), tin octylate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, behene transition metal compounds (transition metal salts) such as zinc compounds such as zinc acid, zinc mystate) and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate, etc.); A blending amount of the curing accelerator is 0.01 to 5.0 parts by weight based on 100 parts of the epoxy resin.

The curable resin composition of the present invention can also contain a phosphorus-containing compound as a component for imparting flame retardancy. The phosphorus-containing compound may be of a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4'-biphenyl (dixylylenyl phosphate) and other phosphoric acid esters; 9,10-dihydro-9-oxa -phosphanes such as 10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes Phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylene bis(dixylylenyl phosphate), 1 ,4-phenylenebis(dixylylenyl phosphate), 4,4'-biphenyl(dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. As for the content of the phosphorus-containing compound, (phosphorus-containing compound)/(total epoxy resin) is preferably in the range of 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardance is insufficient, and if it is more than 0.6, there is a concern that the hygroscopicity and dielectric properties of the cured product may be adversely affected.

Furthermore, a light stabilizer may be added to the curable resin composition of the present invention, if necessary. Hindered amine-based light stabilizers, particularly HALS, are suitable as the light stabilizer. HALS are not particularly limited, but representative ones include dibutylamine/1,3,5-triazine/N,N'-bis(2,2,6,6-tetramethyl-4- Polycondensation product of piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, dimethyl-1-(2-hydroxyethyl)-4-hydroxy succinate -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, bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, and the like. Only one type of HALS may be used, or two or more types may be used in combination.

Furthermore, the curable resin composition of the present invention can be blended with a binder resin, if necessary. Examples of binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. , but 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, preferably 0.05 to 50 parts by mass, more preferably 0.05 to 50 parts by mass based on 100 parts by mass of the resin component. 0.05 to 20 parts by weight are used as needed.

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. , powders such as aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide asbestos, glass powder, etc., or inorganic fillers made of spherical or pulverized powders. can be done. In particular, when obtaining a curable resin composition for semiconductor encapsulation, the amount of the inorganic filler used is usually 80 to 92% by mass, preferably 83 to 90% by mass in the curable resin composition. be.

The curable resin composition of the present invention may optionally contain known additives. Specific examples of additives that can be used include polybutadiene and its modified products, modified acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimide, fluororesins, silicone gels, silicone oils, fillers such as silane coupling agents. Coloring agents such as surface treatment agents for materials, release agents, carbon black, phthalocyanine blue, and phthalocyanine green. The amount of these additives to be added is preferably 1,000 parts by mass or less, more preferably 700 parts by mass or less per 100 parts by mass of the curable resin composition. Polybutadiene and modified products thereof, polyphenylene ether, polystyrene, polyethylene, fluororesins, and the like are preferred from the viewpoint of low water absorption and electrical properties. Polybutadiene and its modified products are preferred from the viewpoint of electrical properties, adhesion and low water absorption. Specifically, for example, butadiene-based thermoplastic elastomers such as styrene-butadiene copolymers (SBR: RICON-100, RICON-181, RICON-184, all manufactured by Clay Valley, etc.), acrylonitrile-butadiene copolymers; 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, etc. Styrene-based thermoplastic elastomers and the like are included. These styrenic thermoplastic elastomers may be used alone or in combination of two or more. Among these high molecular weight substances, styrene-butadiene-styrene copolymer, hydrogenated styrene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, hydrogenated styrene-isoprene-styrene copolymer, hydrogenated styrene (butadiene/isoprene) styrene. Styrenic thermoplastic elastomers such as copolymers are preferred, particularly styrene-isoprene-styrene copolymers, hydrogenated styrene-butadiene-styrene copolymers, hydrogenated styrene-isoprene-styrene copolymers, hydrogenated styrene (butadiene/isoprene)-styrene copolymers. Coalescing is more preferred because it has higher heat resistance and is less prone to oxidative degradation. 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, Septon 8006, Septon 8007L, Septon HG252, Septon V9827, Hybler 7125 (hydrogenated), Hybler 7215F, and Hibler 7311F (all manufactured by Kuraray Co., Ltd.). If it is too much, the compatibility with the polyphenylene ether compound, low molecular weight components with a weight average molecular weight of about 50 to 1000, and oligomer components with a weight average molecular weight of about 1000 to 5000 will deteriorate, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, due to their polarity, among the additives and the curable resin components, etc., they are mainly composed of hydrocarbons. It is difficult to ensure compatibility with low-polarity compounds such as compounds or compounds consisting only of hydrocarbons. On the other hand, the maleimide compound having a polystyrene structure in the molecule according to the present invention does not itself have a skeleton design that actively introduces heteroatoms such as oxygen and nitrogen (there are few polar groups), resulting in low polarity. In addition, it has excellent compatibility with materials having low dielectric properties and compounds composed only of hydrocarbons.

The curable resin composition of the present invention is obtained by uniformly mixing the above-mentioned respective components in a predetermined ratio, usually precured at 130 to 180 ° C. for 30 to 500 seconds, and further cured at 150 to 200 ° C. After curing for 2 to 15 hours at , the curing reaction proceeds sufficiently to obtain the cured product of the present invention. It is also possible to uniformly disperse or dissolve the components of the curable resin composition in a solvent or the like, remove the solvent, and then cure the composition.

The curable resin composition of the present invention thus obtained is useful as an insulating material, a laminate (printed wiring board, BGA substrate, build-up substrate, etc.), a sealing material, a resist, and other electrical and electronic component materials. . 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 encapsulation, solder reflow resistance is beneficial.

A semiconductor device has one encapsulated with the curable resin composition of the present invention. Examples of semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), and TQFP. (think quad flat package) and the like.

The method for preparing 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, a curing agent such as an epoxy resin, an amine compound, a maleimide compound, a cyanate ester compound, a phenol resin, an acid anhydride compound, and other additives may be added for prepolymerization. . Mixing or prepolymerization of each component is carried out by using, for example, an extruder, kneader, rolls, etc. in the absence of a solvent, and by using a reactor equipped with a stirrer in the presence of a solvent.

As a method for uniform mixing, the components are kneaded at a temperature within the range of 50 to 100° C. using a device such as a kneader, a roll, or a planetary mixer to obtain a uniform resin composition. The obtained resin composition is pulverized and then molded into a cylindrical tablet by a molding machine such as a tablet machine, or formed into granular powder or a powdery molding, or these compositions are placed on a surface support. It can also be melted and molded into a sheet having a thickness of 0.05 mm to 10 mm to form a curable resin composition molding. The obtained molded article becomes a non-sticky molded article at 0 to 20.degree.
The resulting molded product 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 prepare a varnish-like 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, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to form a varnish. , Polyester fiber, polyamide fiber, alumina fiber, paper, etc., is impregnated into a base material and heat-dried to obtain a prepreg, which is hot-press molded to obtain a cured product of the curable resin composition of the present invention. . In this case, the solvent is usually used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, it is possible to obtain a curable resin-cured product containing carbon fibers by, for example, the RTM method.

The curable composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility and the like in the B-stage. Such a film-type resin composition is obtained 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-stage. It is obtained as a sheet-like adhesive by This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.

A prepreg can be obtained by heating and melting the curable resin composition of the present invention, reducing the viscosity, and impregnating reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers with the curable resin composition. 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, inorganic fibers other than glass, and poly paraphenylene terephthalamide (Kevlar®, manufactured by DuPont), wholly aromatic polyamides, polyesters; and organic fibers such as polyparaphenylene benzoxazole, polyimides and carbon fibers, but are particularly limited to these. not. The shape of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, and the like. Plain weave, Nanako weave, twill weave, and the like are known as weaving methods of woven fabric, and it is possible to appropriately select and use from these known methods depending on the intended use and performance. In addition, a woven fabric subjected to opening treatment or a glass woven fabric surface-treated with a silane coupling agent or the like is preferably used. Although the thickness of the base material is not particularly limited, it is preferably about 0.01 to 0.4 mm. A prepreg can also be obtained by impregnating reinforcing fibers with the varnish and heating and drying the varnish.

The laminate of the present embodiment includes one or more prepregs. The laminate is not particularly limited as long as it comprises one or more prepregs, and may have any other layers. As a method for producing a laminate, generally known methods can be appropriately applied, and there is no particular limitation. For example, when molding 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 the above prepregs are laminated and heat-pressed to form a laminate. Obtainable. At this time, the heating temperature is not particularly limited, but is preferably 65 to 300°C, more preferably 120 to 270°C. In addition, the pressure to be applied is not particularly limited, but if the pressure is too high, it will be difficult to adjust the solid content of the resin in the laminate and the quality will not be stable. 2.0 to 5.0 MPa is preferable, and 2.5 to 4.0 MPa is more preferable, because it deteriorates. The laminate of the present embodiment can be suitably used as a metal-foil-clad laminate described later by including a layer made of metal foil.
After cutting the prepreg into a desired shape and laminating it with copper foil or the like if necessary, the curable resin composition is heat-cured while applying pressure to the laminate by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. Electrical and electronic laminates (printed wiring boards) and carbon fiber reinforcing materials can be obtained.

The cured product of the present invention can be used in various applications such as molding materials, adhesives, composite materials and paints. Since the cured product of the curable resin composition according to the present invention exhibits excellent heat resistance and dielectric properties, it can be used as a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, a sealing material for organic EL elements, and a printed wiring board. , electrical and electronic parts such as build-up laminates, and composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics.

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

Various analysis methods used in the examples are described below.
<Gel permeation chromatography (GPC)>
A weight average molecular weight (Mw) and a number average molecular weight (Mn) were calculated by polystyrene conversion 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-602x2, KF-601x2)
Linking eluent: Tetrahydrofuran Flow rate: 0.5 ml/min.
Column temperature: 40°C
Detection: RI (differential refraction detector)

・ GC-MS (gas chromatography mass spectrometry) analyzer: JEOL JMS-Q1500GC
Column: Agilent HP-5ms 30m×0.25mm i. d. (Thickness 0.25 μm)
Carrier: He 1.5 mL/min Split 1/30
Injection temperature: 300°C
Oven temperature: 100° C. (2 min)-310° C. (37 min) 10° C./min temperature rise ionization current: 70 eV
Ionization: EI
Sample injection: 1 μL

<Resin physical property measurement conditions>
Amine equivalent A value was measured without using perchloric acid with reference to the method described in JIS K-7236, and the obtained value was taken as the amine equivalent. The unit is g/eq. is.
・Softening point Measured by a method based on JISK-7234, and the unit is °C.
· ICI viscosity is measured by a method based on JISK-7117-2, and the unit is Pa·s.

[Example 1]
100 parts of toluene, 26.0 parts of styrene (manufactured by Tokyo Kasei Co., Ltd.), and 26.5 parts of benzaldehyde (manufactured by Tokyo Kasei Co., Ltd.) while purging with nitrogen in a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer. was added, 3.3 parts of p-toluenesulfonic acid was added, and the mixture was reacted at 120° C. for 4 hours. After allowing to cool to room temperature, 93.1 parts of aniline and 26.1 parts of 35% hydrochloric acid were added, and the internal temperature was raised to 180° C. while extracting water produced by dehydration together with toluene, and the mixture was reacted for 14 hours. After allowing to cool to room temperature, the toluene and water extracted were returned to the system, and 39.2 parts of a 30% aqueous sodium hydroxide solution was added for neutralization. Thereafter, the organic layer was washed with water and concentrated until the waste liquid became neutral to obtain 61.5 parts of amine compound (A1). The amine compound (A1) had an amine equivalent weight of 325.9 g/eq, a softening point of 80.9° C., and an ICI viscosity (150° C.) of 0.08 Pa·s. A chart obtained by GPC analysis (RI) is shown in FIG. GPC analysis revealed a number average molecular weight Mn of 410 and a weight average molecular weight Mw of 521. A GC-MS chart of the target compound is shown in FIG. GC-MS analysis confirmed that the amine compound represented by the 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, condenser and stirrer, and the mixture was heated and stirred until refluxing. 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 for 2 hours under reflux. After allowing to cool, the organic layer was washed four times with 100 parts of water, then returned to the reaction vessel, 2.8 parts of methanesulfonic acid was added again, and the mixture was reacted 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 desired maleimide compound (M-1) as a brown solid resin. A GPC chart of the obtained maleimide compound is shown in FIG. The number average molecular weight Mn was 602 and the weight average molecular weight Mw was 928 by GPC analysis. A GC-MS chart of the target maleimide compound is shown in FIG. According to GC-MS analysis, the number average molecular weight Mn was 410 and the weight average molecular weight Mw was 521 by GPC analysis represented by the formula (1). It was confirmed that the compound was produced.

[Example 3, Comparative Example 1]
Each material was dissolved in acetone in the ratio shown in Table 1 so that the solid content was 50% by mass and blended, pre-dried in a vacuum oven at 60 ° C. for 30 minutes, and dried at 150 ° C. for 1 hour to obtain a powdery resin composition. got After that, a 5 g sample was sandwiched between mirror copper foils (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.) and vacuum press molded, and cured at 220 ° C. for 2 hours (Comparative Example 1 was cured at 175 ° C. for 2 hours. ). At this time, as a spacer, a cushion paper having a thickness of 250 μm was hollowed out in the center to a size of 150 mm in length and width. For the evaluation, a laser cutter was used as necessary to cut out a test piece of a desired size, and the evaluation was performed.

<Permittivity test/dielectric loss tangent test>
Using a 10 GHz cavity resonator manufactured by ATE Co., Ltd., a test was performed by the cavity resonator perturbation method. The sample size was 1.7 mm wide×100 mm long, and the thickness was 0.3 mm.

<Heat resistance (DSC)>
Differential scanning calorimeter: DSC6220 (manufactured by SII Nano Technology Co., Ltd.)
Measurement temperature range: 30-330°C
Heating rate: 10°C/min Atmosphere: Nitrogen (30 mL/min)
Sample amount: 5 mg
Tg: The inflection point of the DSC chart was taken as Tg.
DSC charts of Example 3 and Comparative Example 1 are shown in FIGS. 5 and 6, respectively.

・ NC-3000-L: Biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.)
・DCP: dicumyl peroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 2E4MZ: 2-ethyl-4-methylimidazole (curing accelerator, manufactured by Shikoku Kasei Co., Ltd.)

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

The curable resin composition of the present invention and its cured product can be used as insulating materials for electrical and electronic parts (such as highly reliable semiconductor sealing materials), laminates (such as printed wiring boards, BGA substrates, and build-up substrates), and adhesives. (conductive adhesives, etc.), various composite materials including CFRP, paints, 3D printing, and other applications.

Claims (7)

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

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

(In formula (2), m and n are the number of repetitions, and 0≦m<20 and 1<n<20.) 3. The maleimide compound according to claim 1, which has a weight average molecular weight of 300 to 3,000 as determined by gel permeation chromatography (GPC). A curable resin composition containing the maleimide compound according to any one of claims 1 to 3. 5. 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).

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

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