TW202402737A - Maleimide compound,curable resin compositi0n,and cured product thereof,and amine compound and reaction product of amine compound and maleic anhydride - Google Patents

Abstract

Provided are a maleimide compound, a curable resin composition, a cured product thereof, and an amine compound and a reaction product of an amine compound and maleic anhydride, which are raw materials thereof, having excellent high heat resistance, low dielectric properties, and good curability. The maleimide compound is represented by the following formula (1).

(In the formula (1), each of a plurality of R exists independently and represents a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. X is represented by the following formula (2). m is An integer of 0 to 4, n is the number of repetitions, and the average value n_ave of n satisfies 1 ≦n_ave≦ 20.)

(In the formula (2), each of a plurality of R exists independently and represents a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer of 0 to 4, q represents 0 to represents an integer of 3. r is the number of repetitions, and the average value r_ave of r satisfies 1

r_ave

Description

Maleimine compounds, curable resin compositions and cured products thereof, as well as amine compounds and reaction products of amine compounds and maleic anhydride

The present invention relates to maleimine compounds, curable resin compositions and cured products thereof, as well as amine compounds and reactants of amine compounds and maleic anhydride, which are suitable for use in semiconductor sealing materials and printing. Electrical and electronic components such as wiring boards and build-up laminates, lightweight and high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications.

In recent years, as the application fields of laminate boards equipped with electrical and electronic components have expanded, the characteristics required for them have become broader and more sophisticated. In the past, semiconductor wafers were mainly mounted on metal lead frames, but high-processing power semiconductor wafers such as central processing units (hereinafter referred to as CPUs) are increasingly being mounted on laminates made of polymer materials.

Furthermore, in order to satisfy the heating characteristics which are standard values for heat-resistant laminated boards, a heat resistance (Tg) of at least 160° C. or higher is required (Non-Patent Document 1).

In addition, the fifth generation communication system "5G", which is currently being developed at an accelerated pace, is expected to have further large-capacity and high-speed communications. The demand for low dielectric tangent materials is increasing day by day, requiring a dielectric tangent below 0.005 at least at 10GHz.

Furthermore, in the automotive field, as electronics advances, precision electronic equipment is sometimes installed near the engine drive unit, and therefore a higher level of heat and moisture resistance is required. SiC semiconductors are beginning to be used in trains, air conditioners, etc. Since sealing materials for semiconductor components require extremely high heat resistance, conventional epoxy resin sealing materials cannot meet this requirement.

In view of this background, polymer materials that have both heat resistance and low dielectric tangent properties are being studied. For example, Patent Document 1 proposes a composition including a maleimide resin and a phenol resin having an acryl group. Furthermore, Patent Document 2 discloses an allyl ether resin in which a hydroxyl group is substituted with an allyl group.

In addition, in recent years, 3D printing has attracted much attention as a three-dimensional modeling method. This 3D printing method has begun to be used in aerospace, aerospace, vehicles, and connectors of electronic parts used in these areas that require reliability. in the field. In particular, photocuring and thermosetting resins are being explored for applications represented by stereolithography (SLA) and digital light processing (DLP). Therefore, in the previous methods of transferring from molds, the stability and accuracy of the shape are mainly required, but in 3D printing applications, heat resistance, mechanical properties, toughness, flame retardancy, and even various properties such as electrical properties, and the development of its materials is already underway. In addition, when used in structural members, there is a problem of changes in characteristics due to moisture absorption and the like. Currently, acrylate resins and epoxy resins are used for such purposes.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 04-359911

[Patent Document 2] International Publication No. 2016/002704

[Non-patent document 1] Touo Katayama, "Basic Lecture "Substrate Materials" 5th Heat-Resistant Glass Epoxy Laminated Board", Circuit Technology, Electronics Manufacturing Society, 1993, Vol.8, No.6, p.505-511

However, in a composition containing a maleimide resin and a phenol resin having an acryl group, since phenolic hydroxyl groups that did not participate in the reaction during the curing reaction remain, it is difficult to say that the electrical properties are sufficient.

In addition, in allyl ether resins with allyl groups substituting hydroxyl groups, Claisen rearrangement is shown to occur at 190°C, so it will cause helplessness at 200°C, which is the molding temperature of general substrates. Due to the phenolic hydroxyl group involved in the hardening reaction, the electrical properties cannot be satisfied.

In addition, hardened products of acrylic resins and epoxy resins used in 3D printing contain a large number of ester bonds, ether bonds and hydroxyl groups, resulting in insufficient hygroscopic properties.

The present invention was created in view of such a situation, and its purpose is to provide a maleimide compound, a curable resin composition, and a cured product that have high heat resistance, excellent low dielectric properties, and good curability. As well as the amine compound and the reaction product of the amine compound and maleic anhydride as its raw material.

That is, the present invention relates to the following [1] to [8]. In addition, "(numerical value 1) to (numerical value 2)" in the present invention means including the upper and lower limits thereof.

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

(In formula (1), plural R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. X is represented by the following formula (2). m is an integer from 0 to 4 , n is the number of repetitions, the average n _ave of n conforms to 1≦n _ave ≦20),

(In formula (2), plural R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer from 0 to 4, and q represents an integer from 0 to 3. r is The repeat number and the average r _ave of r satisfy 1≦r _ave ≦20. * indicates the bonding position to the aromatic ring of the aforementioned formula (1)).

[2] A maleimide compound represented by the following formula (3),

( _In formula (3 ₎ ,

(In formula (4), a plurality of R exist independently and represent a hydrocarbon group with a carbon number of 1 to 5. p represents an integer from 0 to 4, r is the repeat number, and the average r _ave of r conforms to 1.1≦ r _ave ≦20. * indicates the bonding position with the aromatic ring of the compound of formula (3)).

[3] The maleimide compound as described in the preceding item [2], wherein in the formula (4), p is 2, and the substitution position of R is relative to the maleimide group. Ortho position.

[4] A curable resin composition containing the maleimide compound described in any one of the preceding paragraphs [1] to [3].

[5] The curable resin composition as described in the preceding paragraph [4], further containing a radical polymerization initiator.

[6] A hardened product obtained by hardening the curable resin composition described in the preceding paragraph [4] or [5].

[7] An amine compound represented by the following formula (5),

(In formula (5), plural R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer from 0 to 4, and q represents an integer from 0 to 3. r is The number of repetitions, the average r _ave of r is consistent with 1≦r _ave ≦20).

[8] A reaction product between the compound described in the preceding item [7] and maleic anhydride.

The cured product of the maleimide compound of the present invention has the characteristics of high heat resistance and excellent low dielectric properties. Therefore, it is a material used for sealing of electrical and electronic parts, circuit substrates, carbon fiber composite materials, etc.

Figure 1 shows a GPC chart of the amine compound of Example 1.

Figure 2 shows a GPC chart of the maleimide compound of Example 1.

Fig. 3 shows a ¹ H-NMR chart of the maleimide compound of Example 1.

Figure 4 shows a GPC chart of the amine compound of Example 2.

Figure 5 shows a GPC chart of the maleimide compound of Example 2.

Fig. 6 shows a ¹ H-NMR chart of the maleimide compound of Example 2.

FIG. 7 shows a GPC chart of the amine compound of Synthesis Example 1.

FIG. 8 shows a GPC chart of the maleimide compound of Synthesis Example 2.

The maleimide compound of this embodiment is represented by the following formula (1).

(In formula (1), plural R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. X is represented by the following formula (2). m is an integer from 0 to 4 , n is the number of repetitions, and the average n _ave of n conforms to 1≦n _ave ≦20.)

(In formula (2), plural R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer from 0 to 4, and q represents an integer from 0 to 3. r is The repeat number and the average r _ave of r satisfy 1 ≦ r _ave ≦ 20. * indicates the bonding position to the aromatic ring of the aforementioned formula (1).)

In the aforementioned formula (1) and the aforementioned formula (2), R is a hydrocarbon group with 1 to 10 carbon atoms or a halogenated alkyl group, but is preferably a hydrocarbon group with 1 to 10 carbon atoms, more preferably a hydrocarbon group with 1 to 5 carbon atoms. Particularly preferred is a hydrocarbon group having 1 to 3 carbon atoms. When R has a small number of carbon atoms, it is difficult to generate molecular vibration when exposed to high frequency. Therefore, in the above description, if it is a hydrocarbon group having 1 to 3 carbon atoms, the electrical characteristics will be particularly excellent.

In the aforementioned formula (1), m is usually an integer from 0 to 4, preferably from 0 to 3, more preferably from 0 to 1, and particularly preferably 0. n is the number of repetitions, and the average n _ave of n usually conforms to 1≦n _ave ≦20, preferably 1.1≦n _ave ≦20, more preferably 1.1≦n _ave ≦18, particularly preferably 1.1≦n _ave ≦15. The average value n _ave of n can be calculated from the value of the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) measurement of the compound represented by the aforementioned formula (1). The number average molecular weight is preferably from 200 to less than 10,000, more preferably from 1,000 to less than 7,500, and particularly preferably from 2,000 to less than 5,000. If the number average molecular weight is less than 10,000, purification by water washing is easy, and if it is 200 or more, the target compound is less likely to volatilize in the solvent distillation step.

In the aforementioned formula (2), p usually represents an integer from 0 to 4, preferably from 0 to 3, and more preferably from 0 to 2. q usually represents an integer from 0 to 3, preferably from 0 to 2, more preferably from 0 to 1, and particularly preferably 0. r is the number of repetitions. The average r _ave of r usually conforms to 1≦r _ave ≦20, preferably 1.1≦r _ave ≦20, more preferably 1.1≦r _ave ≦18, particularly preferably 1.1≦r _ave ≦15.

A preferred aspect of the maleimide compound represented by the aforementioned formula (1) is a maleimide compound represented by the following formula (3).

(In formula ( _{3 )} ,

(In formula (4), a plurality of R exist independently and represent a hydrocarbon group with a carbon number of 1 to 5. p represents an integer from 0 to 4, r is the repeat number, and the average r _ave of r conforms to 1.1≦ r _ave ≦20. * indicates the bonding position to the aromatic ring of the compound of formula (3).)

In the aforementioned formula (4), from the viewpoint of molecular weight control, solvent solubility, dielectric properties, low water absorption, and heat resistance, a particularly preferred one is: R is in the ortho position with respect to the maleimide group. Substitute 2 substituents.

The maleimine compound represented by the aforementioned formula (1) can be obtained, for example, by the reaction of a polymer of an amine compound represented by the following formula (5) and maleic anhydride. The polymerization of the amine compound represented by the following formula (5) and the maleide imidization reaction can be performed separately, but the amine compound of the following formula (5) can be performed once in the presence of an acid catalyst such as methanesulfonic acid. Polymerization reaction and maleic acid imidization reaction. The conditions for the maleide imidization reaction are not particularly limited. Examples of solvents used include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane and n-hexane, diethyl ether, and diisopropyl ether. Water-insoluble solvents such as ethers, ester solvents such as ethyl acetate and butyl acetate, and ketone solvents such as methyl isobutyl ketone and cyclopentanone are not limited to these, and two or more types may be used in combination. . In addition to the above-mentioned water-insoluble solvent, an aprotic polar solvent may be used in combination. Examples include dimethylsulfuric acid, dimethylsulfuric acid, dimethylformamide, dimethylacetylamide, 1,3-dimethyl-2-imidazolinone, N-methylpyrrolidone, and the like. , two or more types can be used together. When an aprotic polar solvent is used, it is preferable to use a water-insoluble solvent with a boiling point higher than that used in combination. During the reaction, if necessary, in terms of catalysts, in addition to hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride, and activated clay can also be used. (activated clay), acidic clay, white carbon, zeolite, silica-alumina (silica-alumina) and other solid acids, acidic ion exchange resin, etc. These systems can be used alone, or two or more types can be used in combination. The amount of catalyst used is usually 0.1 to 0.8 mole, preferably 0.2 to 0.7 mole, relative to 1 mole of the amine group of the amine compound used. If the amount of catalyst used is too much, the viscosity of the reaction solution will be too high, making it difficult to stir. If it is too small, the reaction may proceed slowly. In addition, as a cocatalyst for imidization, an alkaline cocatalyst such as triethylamine can also be used alone or in combination. When sulfonic acid or the like is used as a catalyst, the extraction step can be performed after neutralization with an alkali metal such as sodium hydroxide or potassium hydroxide. For the extraction step, aromatic hydrocarbon solvents such as toluene or xylene can be used alone, or non-aromatic hydrocarbon solvents such as cyclohexane or toluene can be used in combination. After extraction, the organic layer is washed with water until the drainage becomes neutral, and the solvent is distilled off using an evaporator or the like to obtain the desired maleimide compound.

(In formula (5), plural R's exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms. p represents an integer from 0 to 4, and q represents an integer from 0 to 3. r is The number of repetitions, the average r _ave of r is consistent with 1≦r _ave ≦20).

The definition of R in the aforementioned formula (5) and the preferred ranges of p, q, r _ave are the same as those in the aforementioned formula (2).

In the aforementioned formula (5), from the viewpoint of molecular weight control, solvent solubility, dielectric properties, low water absorption, and heat resistance, among the benzene rings bonded to the amine group, p=2 and R are particularly preferred. The substitution positions are two ortho positions relative to the amine group.

The softening point of the amine compound represented by the aforementioned formula (5) is preferably 120°C or lower, more preferably 110°C or lower. If the softening point is 120° C. or lower, the viscosity when derived into the maleimide compound represented by the aforementioned formula (1) becomes low. Thereby, it is easy to ensure the fluidity of the curable resin composition without impairing the impregnability of fibrous materials such as glass cloth and carbon fiber, and it is easy to make the curable resin composition into a semi-cured state by making it into a prepreg or the like ( B stage). Although the viscosity of the curable resin composition can also be reduced by increasing the diluting solvent, in this case, the curable resin composition in the impregnation step may not be fully adhered to the fibrous material. Therefore, it is better to use the aforementioned The softening point of the amine compound represented by formula (5) is 120°C or lower.

The amine compound represented by the aforementioned formula (5) can be prepared, for example, by reacting anilines with excess diisopropenylbenzene (or α, α, α', α'-tetramethylbenzene) in the presence of an acid catalyst. Methanols) are obtained by reacting. In this case, the substituent of the aniline compound is preferably unsubstituted or an alkyl group having 1 to 5 carbon atoms from the viewpoint of molecular weight control, solvent solubility, dielectric properties, low water absorption, and heat resistance. In other words, it is more preferred to be unsubstituted or have two alkyl groups having 1 to 3 carbon atoms in the ortho position of the benzene ring bonded to the amine group.

During synthesis, in addition to liquid acid catalysts such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, p-toluenesulfonic acid, and methanesulfonic acid, Lewis acids such as aluminum chloride and zinc chloride can also be used. Activated clay, acidic clay, white carbon, zeolite, silica-alumina and other solid acid catalysts, acidic ion exchange resin, etc. These acid catalysts may be used alone or in combination of two or more types. Relative to the total weight of diisopropenylbenzene (or α, α, α', α'-tetramethylbenzenedimethanols) and anilines belonging to the reaction matrix, the acid catalyst is used in an amount of 0.01 to 50 wt. %, preferably 0.1 to 35% by weight. If the amount of acid catalyst used is too much, there is a risk of increasing useless waste, and if it is too little, there is a risk of slowing down the reaction. Examples of solvents 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 esters such as ethyl acetate and butyl acetate. Solvents, ketone solvents such as methyl isobutyl ketone, cyclopentanone, etc. Such non-water-soluble solvents are not limited to these, and two or more types may be used in combination. In addition to the above-mentioned water-insoluble solvent, an aprotic polar solvent may be used in combination. Examples include dimethylsulfuric acid, dimethylsulfuric acid, dimethylformamide, dimethylacetylamide, 1,3-dimethyl-2-imidazolinone, N-methylpyrrolidone, and the like. , two or more types can be used together. When using an aprotic polar solvent, it is preferable to use a water-insoluble solvent with a boiling point higher than that used in combination. The reaction temperature is preferably 80 to 250°C, more preferably 90 to 240°C, still more preferably 100 to 230°C. If the reaction temperature is too high, a useless thermal decomposition reaction may occur, and if the reaction temperature is too low, the reaction may not proceed sufficiently. When α,α,α',α'-tetramethylbenzenedimethanol is used as the raw material, or when an acid catalyst containing water is used, the water produced and the water in the system will be heated up while increasing the temperature. It is removed from the system while azeotroping with the solvent. After the reaction is terminated, the acid catalyst is neutralized with an alkaline aqueous solution, etc., then a water-insoluble organic solvent is added to the oil layer and water washing is repeated until the waste water becomes neutral, and then the solvent is removed under heating and reduced pressure. In the case of using activated clay or ion exchange resin, the reaction solution is filtered and the acid catalyst is removed after the reaction is terminated.

Examples of the anilines include aniline, o-toluidine, m-toluidine, p-toluidine, o-ethylaniline, m-ethylaniline, p-ethylaniline, o-propylaniline, m-propylaniline, p-propylaniline, o-isopropylaniline Propylaniline, m-isopropylaniline, p-isopropylaniline, 2,6-dimethylaniline, 2,6-diethylaniline, 2,6-dipropylaniline, 2,6-isopropylaniline, 2- Ethyl-6-methylaniline, 2-propyl-6-methylaniline, 2-isopropyl-6-methylaniline, 2-ethyl-6-propylaniline, 2-ethyl-6- Isopropylaniline, etc., but are not limited to these. These can be used individually or in combination of 2 or more types. If the carbon number is large, the solvent solubility will be improved, but the heat resistance will be reduced, so it is preferably unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms, and more preferably unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms. The alkyl substituted ones are preferably unsubstituted or methyl substituted.

Examples of the aforementioned diisopropenylbenzene include: 1,2-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, and alkyl substituted products thereof. wait.

Examples of the aforementioned α,α,α',α'-tetramethylbenzenedimethanol include: α,α,α',α'-tetramethyl-1,2-benzenedimethanol, α,α,α' , α'-tetramethyl-1,3-benzenedimethanol, α,α,α',α'-tetramethyl-1,4-benzenedimethanol, and alkyl substitutes thereof, etc.

The aforementioned diisopropenylbenzene and the aforementioned α, α, α′, α′-tetramethylbenzenedimethanols may be used individually, or two or more types may be used in combination. The usage amount is preferably 1.0 to 10 times mole, more preferably 1.0 to 7.5 times mole, and still more preferably 1.0 to 5.0 times mole relative to 1 mole of amine group of aniline.

[Polymerization initiator]

The curable resin composition of this embodiment can also be enhanced in curability by adding a polymerization initiator. The polymerization initiator is a compound that can polymerize olefin functional groups such as ethylenically unsaturated bonds, and examples thereof include olefin metathesis polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators. agent and free radical polymerization initiator. Among them, it is preferable to use a radical polymerization initiator having curability and moderate stability. This may occur if it is an olefin metathesis polymerization initiator such as a Schrock catalyst with molybdenum as the central metal, an anionic polymerization initiator such as n-butyllithium (n-BuLi), or a cationic polymerization initiator such as triethylaluminum. Reacts with moisture in the air, resulting in poor stability.

The free radical polymerization initiator refers to a compound that generates free radicals by irradiation or heating with ultraviolet or visible light and initiates a chain polymerization reaction. Examples of free radical polymerization initiators that can be used include organic peroxides, azo compounds, tetraphenyl-1,2-ethylene glycols (Benzopinacol), etc., for controlling the curing temperature or suppressing degassing. , from the viewpoint of having little impact on the electrical properties of decomposed products, it is better to use organic peroxides.

Examples of the above-mentioned organic peroxides include peroxyketones such as methyl ethyl ketone peroxide and acetyl propyl ketone peroxide, diyl peroxides such as benzoyl peroxide, and diisoperoxides. Propylbenzene, 1,3-bis-(tertiary butylperoxyisopropyl)-benzene and other dialkyl peroxides, tertiary butyl peroxybenzoate, 1,1-di-tertiary Peroxyketals such as butyl peroxycyclohexane, α-cumyl peroxyneodecanoate, tertiary butyl peroxyneodecanoate, tertiary butyl peroxypivalate, peroxy-2 -1,1,3,3-tetramethylbutyl ethylhexanoate, tertiary amyl peroxy-2-ethylhexanoate, tertiary butyl peroxy-2-ethylhexanoate, peroxy- Alkyl peroxyesters such as tertiary amyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary amyl peroxybenzoate, etc. , di-2-ethylhexyl peroxydicarbonate, bis(4-tertiary butylcyclohexyl) peroxydicarbonate, tertiary butyl peroxyisopropyl carbonate, 1,6-bis(tertiary) Butyl peroxycarbonyloxy) n-hexane and other peroxycarbonates, tertiary butyl hydroperoxide, cumene hydroperoxide, tertiary butyl peroxyoctanoate, lauryl peroxide, etc., but It is not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used. Among the above-mentioned organic peroxides, preferred are ketone peroxides, diyl peroxides, hydrogen peroxides, dialkyl peroxides, ketal peroxides, alkyl peroxyesters, and peroxyesters. Oxidized carbonates, etc., more preferably dialkyl peroxides.

Examples of the above-mentioned azo compounds include azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). ), etc., but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

The amount of the polymerization initiator to be added is preferably 0.01 to 5 parts by mass when the total amount of non-volatile matter excluding the inorganic filler (filler) in the curable resin composition is 100 parts by mass. Preferably, it is 0.01 to 3 parts by mass. If the amount of the polymerization initiator used is less than 0.01 parts by mass, the molecular weight may not be fully elongated during the polymerization reaction. If it is more than 5 parts by mass, the dielectric properties such as dielectric constant and dielectric tangent may be impaired. The danger.

[Polymerization inhibitor]

The curable resin composition of this embodiment may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability can be improved and the reaction starting temperature can be controlled. Hardening is easily ensured by controlling the reaction starting temperature The fluidity of the resin composition does not impair the impregnability of fibrous materials such as glass cloth or carbon fiber, and facilitates B-stage transformation such as prepreg formation. If the polymerization reaction proceeds excessively during the preparation of prepregs, problems such as difficulty in lamination during the lamination step may easily occur.

The polymerization inhibitor can be added when synthesizing the compound represented by the aforementioned formula (1), or can be added after synthesis. The usage amount of the polymerization inhibitor is 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight relative to 100 parts by weight of the compound represented by the aforementioned formula (1).

Examples of polymerization inhibitors include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitryl radical-based polymerization inhibitors. In addition, a single type of polymerization inhibitor may be used, or a plurality of types may be used in combination. Among these, in this embodiment, a phenol-based, hindered amine-based, nitroso-based, or nitryl radical-based polymerization inhibitor is preferred.

、2,4-雙[(辛硫基)甲基]鄰甲酚等單酚類，2,2’-亞甲基雙(4-甲基-6-三級丁基酚)、2,2’-亞甲基雙(4-乙基-6-三級丁基酚)、4,4’-硫基雙(3-甲基-6-三級丁基酚)、4,4’-亞丁基雙(3-甲基-6-三級丁基酚)、三乙二醇-雙[3-(3-三級丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-正己烷二醇-雙[3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯]、N,N’-六亞甲基雙(3,5-二-三級丁基-4-羥基-氫化肉桂醯胺)、2,2-硫基-二乙烯雙[3-(3,5-二-三級丁基-4-羥基苯基)丙酸酯]、3,5-二-三級丁基-4-羥基苄基膦酸-二乙基酯、3,9-雙[1,1-二甲基-2-{β-(3-三級丁基-4-羥基-5-甲基苯基)丙醯氧基}乙基]2,4,8,10-四氧雜螺[5,5]十一烷、雙(3,5-二-三級丁基-4-羥基苄基磺酸乙基)鈣等雙酚類，1,1,3-參(2-甲基-4-羥基-5-三級丁基苯基)丁烷、1,3,5-三甲基- 2,4,6-參(3,5-二-三級丁基-4-羥基苄基)苯、肆-[亞甲基-3-(3’,5’-二-三級丁基-4’-羥基苯基)丙酸酯]甲烷、雙[3,3’-雙-(4’-羥基-3’-三級丁基苯基)丁酸]乙二醇酯、參-(3,5-二-三級丁基-4-羥基苄基)-異氰脲酸酯、1,3,5-參(3’,5’-二-三級丁基-4’-羥基苄基)-S-三

-2,4,6-(1H,3H,5H)三酮、生育酚等高分子型酚類等，惟並非限於此等者。 Examples of the phenolic polymerization inhibitor include 2,6-di-tertiary butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tertiary butyl-p-ethylphenol, β-(3, 5-Di-tertiary butyl-4-hydroxyphenyl)stearyl propionate, 3-(3,5-di-tertiary butyl-4-hydroxyphenyl) isooctyl propionate, 2,4 -Bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tertiary butylaniline)-1,3,5-tertiary

, 2,4-bis[(octylthio)methyl]o-cresol and other monophenols, 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2,2 '-Methylenebis(4-ethyl-6-tertiary butylphenol), 4,4'-Thiobis(3-methyl-6-tertiary butylphenol), 4,4'-ethylene Bis(3-methyl-6-tertiary butylphenol), triethylene glycol-bis[3-(3-tertiary butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-n-hexanediol-bis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3,5 -Di-tertiary butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-tertiary butyl-4-hydroxyphenyl)propanol acid ester], 3,5-di-tertiary butyl-4-hydroxybenzylphosphonic acid-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3- Tertiary butyl-4-hydroxy-5-methylphenyl)propyloxy}ethyl]2,4,8,10-tetraxaspiro[5,5]undecane, bis(3,5 -Di-tertiary butyl-4-hydroxybenzyl sulfonate ethyl) calcium and other bisphenols, 1,1,3-gin (2-methyl-4-hydroxy-5-tertiary butylphenyl) Butane, 1,3,5-trimethyl-2,4,6-shen(3,5-di-tertiary butyl-4-hydroxybenzyl)benzene, 4-[methylene-3-( 3',5'-Di-tertiary butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tertiary butylphenyl )butyric acid] ethylene glycol ester, gin-(3,5-di-tertiary butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-gin(3',5'- Di-tertiary butyl-4'-hydroxybenzyl)-S-tri

-2,4,6-(1H,3H,5H)triketone, tocopherol and other high molecular phenols, but not limited to these.

Examples of the sulfur-based polymerization inhibitor include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and disulfide 3,3'-thiodipropionate. Fatty esters, etc., but not limited to these.

Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, nonyl phenyl phosphite, and diisodecyl phosphite. Neopentyl erythritol phosphite, 2,4-di-tertiary butylphenyl phosphite, cyclic neopentane tetrakis(octadecyl) phosphite, cyclic neopentane Tetrakis(2,4-di-tertiary butylphenyl)phosphite, cyclic neopentane tetrabis(2,4-di-tertiary butyl-4-methylphenyl)phosphite Phosphites such as esters, bis[2-tertiary butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite, 9,10-di Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tertiary butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa -10-Phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and other oxaphosphaphenanthrene oxides, etc. , but it is not limited to these.

Examples of the hindered amine polymerization inhibitor include Adekastab LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab 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 to these.

Examples of the nitroso-based polymerization inhibitor include p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxylamine (cupferron), etc. It is not limited to these. Among these, the ammonium salt of N-nitrosophenylhydroxylamine (cupferrite) is preferred.

Examples of the nitroxyl radical polymerization inhibitor include di-tertiary butyl nitrogen oxide, 2,2,6,6-tetramethylpiperidine-1-oxide, and 4-hydroxy-2,2 ,6,6-tetramethylpiperidine-1-oxide, 4-side oxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-amino-2,2, 6,6-Tetramethylpiperidine-1-oxide, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxide, 4-acetyloxy-2,2 ,6,6-tetramethylpiperidine-1-oxide, 4-benzyloxy-2,2,6,6-tetramethylpiperidine-1-oxide, etc., but are not limited to these .

[Inorganic filler]

The curable resin composition of this embodiment may contain an inorganic filler. Examples of the inorganic filler include fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, oxide Zirconium, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titanium dioxide, talc, clay, iron oxide asbestos, glass powder and other powders, or made of these Spherical shapes or pulverized inorganic fillers, etc., but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

When obtaining a curable resin composition for sealing a semiconductor, the usage amount of the inorganic filler is preferably 80 to 92 parts by mass, and more preferably 83 to 90 parts by mass in 100 parts by mass of the curable resin composition. . In addition, when obtaining a curable resin composition for interlayer insulating layer forming materials, copper-clad laminates or prepregs, RCC and other substrate materials, in 100 parts by mass of the curable resin composition, one of the above-mentioned inorganic fillers The usage amount is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass.

[Harding accelerator]

The curable resin composition of this embodiment can improve curability by adding a curing accelerator. The hardening accelerator is preferably an anionic hardening accelerator that generates anions by irradiation or heating of ultraviolet or visible light to accelerate the curing reaction, or an anionic curing accelerator that generates cations by irradiation or heating of ultraviolet or visible light to accelerate hardening. Reactive cationic hardening accelerator.

Examples of the anionic hardening accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4 -Dimethylaminopyridine, benzyldimethylamine, 2,4,6,-shen(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)- Undecene and the like, preferably 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene. In addition, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecyl ammonium salt, hexadecyltrimethylammonium salt, cetyltrimethylammonium salt, etc. can be cited. Methyl ammonium hydroxide and other 4th grade ammonium salts.

Examples of cationic hardening accelerators include 4th-level phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counter ions of the 4th-level salt are halogen, organic acid ions, and hydroxide Although not specifically designated, organic acid ions, hydroxide ions, etc. are particularly preferred, tin octoate, zinc carboxylate (zinc 2-ethyl n-hexanoate, zinc stearate, zinc behenate, Transition metal compounds (transition metal salts) such as zinc myristate), zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), etc., but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

The compounding amount of the hardening accelerator is 0.01 to 5.0 parts by mass based on necessity, relative to 100 parts by mass of the total non-volatile matter excluding inorganic fillers (fillers) in the curable resin composition.

[Flame retardant]

The curable resin composition of this embodiment may use a flame retardant. Examples of flame retardants include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), phosphorus-based flame retardants, etc. To achieve halogen-free flame retardancy, From a viewpoint, a phosphorus-based flame retardant is preferable.

The above-mentioned phosphorus-based flame retardant may be a reactive type or an additive type. Specific examples include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(xylyl)phosphate, cresol diphenyl phosphate, and cresol-di-2,6-xylyl phosphate. Ester, 1,3-phenylenebis(di(dylyl)phosphate), 1,4-phenylenebis(di(dylyl)phosphate), 4,4'-biphenyl(di(dimethylphenyl)phosphate) (xylyl)ester) and other phosphates, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl)-10H-9 - Phosphanes such as oxa-10-phosphaphenanthrene-10-oxide, and phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the aforementioned phosphoranes, red phosphorus, etc., but not Limited to these. In addition, one type of these systems may be used, or a plurality of types may be used. Among the above-mentioned exemplified substances, phosphates, phosphanes, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(di(xylyl)phosphate), 1,4- Phenylene bis(di(xylyl)phosphate), 4,4'-biphenyl(di(dylyl)phosphate), or phosphorus-containing epoxy compounds.

When the total amount of non-volatile matter excluding inorganic fillers (fillers) in the curable resin composition is 100 parts by mass, the content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass. If it is less than 0.1 parts by mass, the flame retardancy may become insufficient. If it exceeds 0.6 parts by mass, the hygroscopicity and dielectric properties of the cured material may be adversely affected.

[Light stabilizer]

/N,N’-雙(2,2,6,6-四甲基-4-哌啶基-1,6-六亞甲基二胺與N-(2,2,6,6-四甲基-4-哌啶基)丁基胺之反應物、 丁二酸二甲基-1-(2-羥基乙基)-4-羥基-2,2,6,6-四甲基哌啶反應物、聚[{6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三

-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亞胺基}六亞甲基{(2,2,6,6-四甲基-4-哌啶基)亞胺基}]、雙(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-雙(1,1-二甲基乙基)-4-羥基苯基]甲基]丙二酸丁酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)2-(3,5-二-三級丁基-4-羥基苄基)-2-正丁基丙二酸酯等，惟並非限於此等者。此外，此等係可使用1種，亦可使用複數種。 The curable resin composition of this embodiment may use a light stabilizer. As the light stabilizer, hindered amine light stabilizers are suitable, and HALS (Hindered Amine Light Stabilizers) and the like are particularly suitable. Examples of HALS include dibutylamine/1,3,5-tris

/N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl Reaction of dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Material, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri

-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl- 4-piperidinyl)imino}], bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl methyl)-4-hydroxyphenyl]methyl]butyl malonate, 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-piperidinyl)2-(3,5-di-tertiary butyl-4-hydroxybenzyl)-2-n-butylpropanyl Diacid esters, etc., but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

When the total amount of nonvolatile matter excluding inorganic fillers (fillers) in the curable resin composition is 100 parts by mass, the content of the light stabilizer is preferably in the range of 0.001 to 10 parts by mass. If it is less than 0.001 parts by mass, the light stabilizing effect may not be fully exerted. If it is more than 10 parts by mass, the hygroscopicity and dielectric properties of the cured material may be adversely affected.

[Binder resin]

The curable resin composition of this embodiment may use a binder resin. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, and silicone resin. Resin, etc., but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

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. If the total non-volatile content of the cured resin composition is 100 after excluding the inorganic filler (filler) In the case of parts by mass, it is preferably 0.05 to 50 parts by mass, more preferably 0.05 to 20 parts by mass.

[Additive]

The curable resin composition of this embodiment may use additives. Examples of additives include modified products of acrylonitrile copolymer, surface treatment agents for fillers such as polyethylene, fluororesin, polysilicone gel, polysilicone oil, and silane coupling agents, release agents, carbon black, and phthalocyanine blue. , phthalocyanine green and other colorants.

The compounding amount of the additive is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less based on 100 parts by mass of the curable resin composition.

In the curable resin composition of this embodiment, epoxy resins, active ester compounds, phenol resins, amine resins, maleimide compounds, compounds having ethylenically unsaturated bonds, isocyanate resins, and Polyamide resin, polyimide resin, cyanate ester resin, polyphenylene ether compound, polybutadiene and its modified products, polystyrene and its modified products, etc., one of these can be used, or Plural types can be used. Among these compounds, in terms of the balance between heat resistance, adhesion and dielectric properties, compounds containing ethylenically unsaturated bonds, cyanate ester resins, polyphenylene ether compounds, polybutylene ether compounds are preferred. Alkene and its modifications, polystyrene and its modifications. By containing these compounds, the brittleness of the hardened material can be improved and the adhesion to the metal can be improved, thereby inhibiting package cracking during reflow soldering or during reliability tests such as hot and cold cycles.

Unless otherwise specified, the usage amount of the above compound 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 compound represented by formula (1). Scope. In addition, a preferable lower limit value is 0.1 mass times or more, more preferably 0.25 mass times or more, and still more preferably 0.5 mass times or more. By setting it within the above range, the effects of the heat resistance and dielectric properties of the compound represented by the aforementioned formula (1) can be exerted, and the effects of each added compound can be added. For these components, those exemplified below can be used.

〔Epoxy resin〕

As for the epoxy resin, although the following examples are preferred, the examples are not limited to these. Moreover, the nature of the epoxy resin may be liquid or solid, and one type may be used or a plurality of types may be used in combination.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, Glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, shrinkage Glyceryl amine type epoxy resin, and epoxy resin with butadiene structure, etc. Specific examples include: "RE310S", "RE410S" (the above are bisphenol A-type epoxy resins manufactured by Nippon Kayaku Co., Ltd.), "RE303S", "RE304S", "RE403S", "RE404S" (the above are bisphenol A-type epoxy resins manufactured by Nippon Kayaku Co., Ltd.) Bisphenol F-type epoxy resin manufactured by Chemical Company), "HP4032", "HP4032D", "HP4032SS" (the above are naphthalene-type epoxy resin manufactured by DIC Company), "828US", "jER828EL", "825" , "828EL" (the above is a bisphenol A-type epoxy resin manufactured by Mitsubishi Chemical Corporation), "jE807", "1750" (the above is a bisphenol F-type epoxy resin manufactured by Mitsubishi Chemical Corporation), "jER152" (Mitsubishi Chemical Corporation Phenol novolac type epoxy resin manufactured by Chemical Company), "630", "630LSD" (the above is glycidylamine type epoxy resin manufactured by Mitsubishi Chemical Company), "ZX1059" (double epoxy resin manufactured by Nippon Steel & Sumitomo Metal Chemical Company) A mixture of phenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (glycidyl ester type epoxy resin manufactured by Nagase ChemteX Co., Ltd.), "CELLOXIDE 2021P" (manufactured by DAICEL Co., Ltd. Alicyclic epoxy resin with ester skeleton), "PB-3600" (epoxy resin with butadiene structure manufactured by DAICEL), "ZX1658", "ZX1658GS" (the above are manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. Liquid 1,4-glycidylcyclohexane type epoxy resin), etc. One type of these may be used alone, or two or more types may be used in combination.

As for the solid epoxy resin, preferred are dixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, and dicyclopentadiene type epoxy resin. , ginseng phenol Type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, onion type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, Examples of the tetraphenylethane-type epoxy resin include naphthol-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, and biphenyl-type epoxy resin. Specific examples include: "HP4032H" (naphthalene-type epoxy resin manufactured by DIC), "HP-4700", "HP-4710" (the above is naphthalene-type tetrafunctional epoxy resin manufactured by DIC), "N -690" (cresol novolac epoxy resin manufactured by DIC), "N-695" (cresol novolac epoxy resin manufactured by DIC), "HP-7200" (dicyclopentadiene manufactured by DIC type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (the above is dicyclopentadiene type epoxy resin manufactured by DIC Corporation), "EXA-7311", "EXA-7311 -G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (the above are naphthyl ether type epoxy resins manufactured by DIC Corporation), "EPPN-502H" (Japanese (Naphthol-cresol novolak type epoxy resin manufactured by Nippon Chemical Company), "NC-7000L", "NC-7300" (the above are naphthol-cresol novolak type epoxy resin manufactured by Nippon Kayaku Company), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (the above are biphenyl aralkyl epoxy resins manufactured by Nippon Kayaku Co., Ltd.), "XD-1000-2L", "XD-1000- L", " Phenolic epoxy resin), "ESN485" (naphthol phenolic epoxy resin manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), "YX-4000H", "YX-4000", "YL6121" (the above are manufactured by Mitsubishi Chemical Corporation biphenyl-type epoxy resin), "YX-4000HK" (bixylenol-type epoxy resin manufactured by Mitsubishi Chemical Corporation), "YX-8800" (onion-type epoxy resin manufactured by Mitsubishi Chemical Corporation), "PG -100", "CG-500" (bisphenol AF type epoxy resin produced by Osaka Gas Chemical Co., Ltd.), "YL-7760" (bisphenol AF type epoxy resin produced by Mitsubishi Chemical Co., Ltd.), "YL-7800" (Mitsubishi Chemical Co., Ltd. Bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation) "jER1010" (solid bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation), "jER1031S" (tetraphenylethane type epoxy resin manufactured by Mitsubishi Chemical Corporation), etc. One type of these may be used alone, or two or more types may be used in combination.

[Active ester compound]

The active ester compound means a compound containing at least one ester bond in the structure and an aliphatic chain, aliphatic ring or aromatic ring bonded to both sides of the ester bond. Examples of active ester compounds include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, and, It is obtained by condensation reaction of at least one compound among a carboxylic acid compound, a chelate chloride or a sulfur carboxylic acid compound, and at least one compound among a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferably obtained from a carboxylic acid compound or a chloride and a hydroxy compound, and the hydroxy compound is preferably a phenol compound or a naphthol compound. One type of active ester compound may be used alone, or two or more types may be used in combination.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromelonic acid, and the like.

Examples of the above-mentioned acid chloride include: acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl acid chloride, succinic acid dichloride, diglylamino acid chloride, glutaryl dichloride, suberyl dichloride, Decanediyl dichloride, hexadiyl dichloride, dodecanediyl dichloride, nonyl dichloride, 2,5-furandicarbonyl dichloride, phthalyl chloride, isophthalyl chloride, p-phenylene Dimethyl chloride, trimesylidene chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzyldichloride, etc.

Examples of the above-mentioned phenol compound and the above-mentioned naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalin (Phenolphthalin), methylated bisphenol A, and methane. Sylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, phloroglucin, dicyclopentadiene-type diphenol compound, phenol novolac, phenol resin described below, etc. Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing one molecule of dicyclopentadiene and two molecules of phenol.

Preferable specific examples of the active ester compound 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 acetate of phenolic novolac, and a benzene compound containing a phenolic novolac. Active ester compounds of formate compounds, compounds described in Example 2 of International Publication No. 2020/095829, compounds disclosed in International Publication No. 2020/059625, etc. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called dicyclopentadiene-type diphenol structure represents a divalent structural unit composed of a phenylene group-dicyclopentene-phenylene group.

Regarding commercially available active ester compounds, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H" -65TM", "EXB-8000L-65TM", "EXB-8150-65T" (manufactured by DIC Corporation). Examples of active ester compounds containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC Corporation), which contains phenolic phenolic aldehydes. Examples of the active ester compound of the acyl compound include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of the active ester compound of the benzyl acyl compound containing phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation). Examples of active ester-based hardeners that are "acetyl compounds of phenolic novolac" include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of active ester-based hardeners containing phosphorus atoms include "EXB-9050L-62M" manufactured by DIC Corporation, etc. .

Regarding the blending ratio of the active ester compound and the epoxy resin, the ratio (α/β) of the active ester equivalent (α) to the epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and still more preferably 0.90 to 1.10. If it is outside the above range, there is a risk that too many epoxy groups or active ester groups will remain in the system. High temperature exposure tests (150°C, 1000 hours, etc.) or long-term reliability tests under high temperature and high humidity conditions (temperature 85°C, humidity 85%, etc.) may lead to deterioration in characteristics.

[Phenol resin]

Phenolic resin means a compound having two or more phenolic hydroxyl groups in the molecule. Examples of the phenolic resin include reactants of phenols and aldehydes, reactants of phenols and diene compounds, reactants of phenols and ketones, reactants of phenols and substituted biphenyls, and reactants of phenols and hydrocarbons. Reactants of substituted phenyls, reactants of bisphenols and aldehydes, etc., but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

Specific examples of each of the above-mentioned raw materials are illustrated below, but are not limited to these.

<Phenols>

Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxybenzene Naphthalene etc.

<Aldehydes>

Formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamic aldehyde, furfural, etc.

<diene compound>

Dicyclopentadiene, terpenes, vinylcyclohexene, norbornanediene, vinylnorbornane, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butyl Diene, isoprene, etc.

<Ketones>

Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, quinone, etc.

<Substituted biphenyls>

4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxy Methyl)-1,1'-biphenyl, etc.

<Substituted phenyls>

1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[Amine resin]

Amine resin means a compound having two or more amine groups in the molecule. Examples of the amine resin include diaminodiphenylmethane, diaminodiphenylmethane, isophoronediamine, naphthalenediamine, aniline phenolic (the reaction product of aniline and formalin), N-methylaniline phenolic ( The reactant of N-methylaniline and formalin), o-ethylaniline phenolic (the reactant of o-ethylaniline and formalin), the reactant of 2-methylaniline and formalin, 2,6-diisopropyl The reactant of 2,6-diethylaniline and formalin, the reactant of 2,6-diethylaniline and formalin, the reactant of 2-ethyl-6-ethylaniline and formalin, the reactant of 2,6-dimethylaniline and formalin Reactants of formalin, aniline resin obtained from the reaction of aniline and xylene chloride, aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)) described in Japanese Patent No. 6429862 - Reactants of 1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), aniline and substituted phenyls (1,4-bis (Chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene, etc.), 4,4'-(1,3-phenylene) Diisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylene)bisaniline, reactants of aniline and diisopropenylbenzene, dimerdiamine, etc., only It is not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

[Maleimine compounds other than maleimide compounds represented by formula (1)]

The maleimide compound means a compound having one or more maleimide groups in the molecule. The curable resin composition of this embodiment may further contain a maleimide compound other than the maleimide compound represented by formula (1). About the maleic imine compound represented by formula (1) Examples of maleimide compounds other than those of Maleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'- Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenyl Ether bis-maleyl imide, 4,4'-diphenyl bis-maleyl imide, 1,3-bis(3-maleyl imide phenoxy)benzene, 1,3-Bis(4-maleimidephenoxy)benzene), Xyloc-type maleimide compound (ANILIX maleimide, manufactured by Mitsui Chemicals FINE Co., Ltd.), Phenyl aralkyl type maleimide compound (described in Example 4 of Japanese Patent Application Laid-Open No. 2009-001783), by placing a resin solution containing a maleimide compound (M2) under reduced pressure. The solvent is distilled off and solidified), bisaminocumylbenzene-type maleimide (maleimide compound described in International Publication No. 2020/054601), Japanese Patent No. 6629692 Or the maleimide compound with an indene structure described in International Publication No. 2020/217679, MATERIAL STAGE, Vol. 18, No. 12, 2019『~Continued‧Epoxy Resin CAS Number Story~Hardening Agent CAS Numbering Memorandum Chapter 31 Bismaleimide (1)", and MATERIAL STAGE, Vol.19, No.2, 2019 "~Continued‧ Epoxy Resin CAS Numbering Story ~ Hardener CAS Numbering Memorandum Chapter 32 However, it is not limited to the maleimide compounds disclosed in "Bismaleimide (2)" and the like. In addition, one type of these systems may be used, or a plurality of types may be used.

The amount of the maleimide compound other than the maleimide compound represented by the formula (1) is preferably added to the maleimide compound represented by the formula (1). 10 mass times or less, more preferably 5 mass times or less, particularly preferably 3 mass times or less. In addition, a preferable lower limit value is 0.01 mass times or more, and more preferably 0.1 mass times or more. If it is within the above range, the effects of heat resistance, dielectric properties, and low water absorption properties of the compound represented by the aforementioned formula (1) can be exerted.

[Compounds with ethylenically unsaturated bonds]

The compound having an ethylenically unsaturated bond means a compound having one or more ethylenically unsaturated bonds polymerizable by heat or light in the molecule regardless of whether a polymerization initiator is used or not.

Examples of the compound having an ethylenically unsaturated bond include the aforementioned phenol resin and a halogen compound having an ethylenically unsaturated bond (chloromethylstyrene, allyl chloride, methallyl chloride, acryl chloride , methacrylic acid chloride, etc.), phenols with ethylenically unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol , isoeugenol, etc.) and halogen compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4 , 4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanogen chloride, etc.), epoxy resin or alcohol and (meth)acrylic acid (acrylic acid, Methacrylic acid, etc.), and acid modified products thereof, but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

[Isocyanate resin]

Isocyanate resin means a compound having two or more isocyanate groups in the molecule. Examples of the isocyanate resin include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4, Aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, naphthalene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate , aliphatic or alicyclic diisocyanates such as norbornene diisocyanate and lysine diisocyanate, biurets of one or more isocyanate monomers, or trimerization of the above diisocyanate compounds Polyisocyanates such as polyisocyanates obtained by the isocyanate compound and polyisocyanates obtained by the urethanation reaction of the above-mentioned isocyanate compounds and polyol compounds are not limited to these. In addition, one type of these may be used. Plural types can be used.

[Polyamide resin]

唑啉中之任1種以上與二羧酸之反應物、二胺與醯氯之反應物、內醯胺化合物之開環聚合物。此外，此等係可使用1種，亦可使用複數種。 Examples of polyamide resin include: diamine, diisocyanate,

Reactants of any one or more oxazolines with dicarboxylic acids, reactants of diamines and chloride, and ring-opening polymers of lactam compounds. In addition, one type of these systems may be used, or a plurality of types may be used.

Specific examples of each of the above-mentioned raw materials are illustrated below, but are not limited to these.

<Diamine>

Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine Amine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine Alkanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, dimerdiamine , cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylenediamine, norbornenediamine, isophoronediamine Amine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethyl methylphenyl)methanebis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-o-methylaniline, 4,4'-methylenebis-o-methylaniline Ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylaniline Ethyldiphenylamine, diaminodiphenyl sulfide, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) )benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-amine hydroxyphenoxy)phenyl]propane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4' -(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylene)bisaniline, 9,9-bis(4-amino) Phenyl) fluorine, 2,7-diamino fluorine, amino benzyl amine, diamino benzophenone, etc.

<Diisocyanate>

Phylene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl) )methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, bicyclo Hexylmethane-4,4'-diisocyanate, etc.

<Dicarboxylic acid>

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid Formic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, sodium 5-isophthalic acid sulfonate, hexahydrocerephthalic acid Dicarboxylic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxyldiphenyl ether, 4, 4'-Dicarboxydiphenyl sulfide, etc.

<Chloride>

Acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, digylamine chloride, glutadiyl dichloride, octadienyl dichloride, hexanediyl dichloride Dichloride, dodecanediyl chloride, nonyl chloride, 2,5-furandicarbonyl dichloride, phthalyl chloride, isophthalyl chloride, terephthalyl chloride, trimethyl Cyl chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, 4,4'-azodibenzyl chloride, etc.

<Lactamide>

ε-caprolactam, ω-undecylactam, ω-laurolactam, etc.

[Polyimide resin]

Examples of the polyimide resin include, but are not limited to, reactants of the aforementioned diamines and the tetracarboxylic dianhydride exemplified below. In addition, one type of these systems may be used, or a plurality of types may be used.

<Tetracarboxylic dianhydride>

4,4'-(Hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dilateral oxytetrahydro-3-furyl)-3-methyl-cyclohexene-1 ,2-dicarboxylic anhydride, pyromelite dianhydride, 1,2,3,4-pyromellitic dianhydride, 3,3',4,4'-diphenylmethyl Ketotetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4 '-Diphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-phenylenetetracarboxylic dianhydride Ethyl-4,4'-diphthalic dianhydride, 2,2'-propylene-4,4'-diphthalic dianhydride, 1,2-ethyl-4,4' -Diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride Anhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic acid Dicarboxylic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4 -Dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)- 2-propyl]phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]phthalic anhydride, bis[3-(3,4-dicarboxyphenoxy) methyl)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 Anhydride, 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-naphthalene tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,3,6,7 -Onion tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride), cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride , 3,3',4,4'-biscyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'- Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene dianhydride Ethyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride , Sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid Dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octan-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'- dione), 4-(2,5-bisoxytetrahydrofuran-3-yl)-1,2,3,4- Tetralin-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride), 9 , 9'-Bis(3,4-dicarboxyphenyl) dianhydride, etc.

[Cyanate ester resin]

The cyanate ester resin is a cyanate ester compound obtained by reacting a phenol resin and a cyanogen halide. Specific examples thereof include benzene dicyanate, benzene tricyanato, naphthalene dicyanate, and biphenyl dicyanate. 2,2'-bis(4-cyanophenyl)propane, bis(4-cyanophenyl)methane, bis(3,5-dimethyl-4-cyanophenyl)methane, 2 ,2'-bis(3,5-dimethyl-4-cyanophenyl)propane, 2,2'-bis(4-cyanophenyl)ethane, 2,2'-bis(4 -Cyanatophenyl)hexafluoropropane, bis(4-cyanophenyl)terine, bis(4-cyanophenyl)thioether, phenolic novolac cyanate, phenol-dicyclopentadiene The hydroxyl group of the co-condensate is converted into a cyanate ester group, but it is not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used.

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

環，氰酸酯樹脂中可含有環烷酸鋅、環烷酸鈷、環烷酸銅、環烷酸鉛、辛酸鋅、辛酸錫、乙醯丙酮鉛、順丁烯二酸二丁基錫等觸媒。 In order to meet the needs, the cyanate group can be trimerized to form homotrimeric

Ring, cyanate ester resin may contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetyl acetonate, dibutyl tin maleate, etc. .

It is preferable to use 0.0001 to 0.10 parts by mass of the catalyst relative to 100 parts by mass of the cyanate ester resin, and preferably 0.00015 to 0.0015 parts by mass.

[Polyphenylene ether compound]

Regarding the polyphenylene ether compound, from the viewpoint of heat resistance and electrical properties, a polyphenylene ether compound having an ethylenically unsaturated bond is preferred, and a polyphenylene ether compound having an acryl group, a methacryloyl group, or Polyphenylene ether compound with styrene structure. Examples of commercially available products include SA-9000 (manufactured by SABIC Co., Ltd., containing methylpropyl A polyphenylene ether compound with an enyl group) and OPE-2St 1200 (a polyphenylene ether compound with a styrene structure manufactured by Mitsubishi Gas Chemical Co., Ltd.), etc.

The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, still more preferably 2000 to 4000. If the molecular weight is less than 500, there is a tendency that a cured product with sufficient heat resistance cannot be obtained. In addition, if the molecular weight exceeds 5,000, the melt viscosity becomes high and sufficient fluidity cannot be obtained, thereby tending to cause molding defects. In addition, the reactivity also decreases, the curing reaction takes a long time, the amount of unreacted substances increases because it is not included in the curing system, the glass transition temperature of the cured product decreases, and the heat resistance of the cured product tends to decrease.

If the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it can maintain excellent dielectric properties and exhibit excellent heat resistance, formability, etc. In addition, here, the number average molecular weight can be specifically measured using gel permeation chromatography or the like.

The polyphenylene ether compound may be obtained by polymerization reaction, or may be obtained by subjecting a high molecular weight polyphenylene ether compound having a number average molecular weight of approximately 10,000 to 30,000 to a redistribution reaction. In addition, radical polymerizability can be provided by reacting these as raw materials with compounds having an ethylenically unsaturated bond such as methacrylic acid chloride, acrylic acid chloride, and chloromethylstyrene. The polyphenylene ether compound obtained by the redistribution reaction is, for example, redistributed by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator. Obtained by reaction. The polyphenylene ether compound obtained by such a redistribution reaction has hydroxyl groups derived from "phenolic compounds that facilitate hardening" at both ends of the molecular chain, so it can further maintain high heat resistance and even After being modified with a compound having an ethylenically unsaturated bond, it is also preferable to introduce functional groups at both ends of the molecular chain. In addition, a polyphenylene ether compound obtained by a polymerization reaction is preferable because it exhibits excellent fluidity.

The molecular weight of the polyphenylene ether compound can be adjusted by adjusting polymerization conditions, etc., if it is a polyphenylene ether compound obtained by a polymerization reaction. In addition, when it is a polyphenylene ether compound obtained by a redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of a redistribution reaction, etc. More specifically, adjustment of the compounding amount of the phenolic compound used in the redistribution reaction, etc. may be considered. That is, the greater the blending amount of the phenolic compound, the lower the molecular weight of the polyphenylene ether compound obtained. At this time, as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction, poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used. In addition, the phenolic compound used in the aforementioned redistribution reaction is not particularly limited, but it is preferable to use polyfunctional phenols having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, cresol novolac, etc. system compound. These systems can be used individually, or two or more types can be used in combination.

The content of the polyphenylene ether compound is not particularly limited, but it is preferably 5 to 1000 parts by mass, and more preferably 10 to 750 parts by mass based on 100 parts by mass of the compound represented by formula (1). If the content of the polyphenylene ether compound is within the above range, it is preferable because it not only has excellent heat resistance and the like, but also can obtain a cured product that fully exhibits the excellent dielectric properties of the polyphenylene ether compound.

[Polybutadiene and its modified products]

Polybutadiene and its modified products refer to compounds having polybutadiene or a structure derived from polybutadiene in the molecule. Regarding the structure derived from polybutadiene, some or all of the unsaturated bonds can be changed into single bonds by hydrogenation.

Examples of polybutadiene and modified products thereof include polybutadiene, hydroxyl-terminated polybutadiene, terminal (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, and amine-terminated polybutadiene. Diene, styrene butadiene rubber, etc., but not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used. Among these, from the viewpoint of dielectric properties, polybutadiene or styrene-butadiene rubber is preferred. Styrene Examples of butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by CRAY VALLEY Co., Ltd.), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), and polybutadiene. B-1000, B-2000, B-3000 (all made by Soda Corporation of Japan), etc. Regarding the molecular weight of polybutadiene and styrene-butadiene rubber, the weight average molecular weight is preferably 500 to 10,000, more preferably 750 to 7,500, and still more preferably 1,000 to 5,000. If it is below the lower limit of the above range, the amount of volatilization will be large, making it difficult to adjust the solid content when preparing a prepreg. If it is above the upper limit of the above range, the compatibility with other curable resins will deteriorate. Generally speaking, in the case of compounds containing heteroatoms such as oxygen or nitrogen, such as bismaleimide or polymaleimide, it is difficult to ensure that they are composed mainly of hydrocarbons due to their polarity. The compatibility of low polar compounds with compounds or compounds consisting only of hydrocarbons. On the other hand, the compound represented by the aforementioned formula (1) has a skeleton design in which heteroatoms such as oxygen or nitrogen are not actively introduced, so it is composed of materials with low polarity and low dielectric properties or only hydrocarbons. The compounds also have excellent compatibility.

The content of polybutadiene and its modified products is not particularly limited, but it is preferably 5 to 1000 parts by mass, more preferably 10 to 750 parts by mass based on 100 parts by mass of the compound represented by formula (1). . When the polybutadiene and its modified products are in the above range, not only are they excellent in heat resistance and the like, but a cured product that fully exhibits the excellent dielectric properties of the polybutadiene and its modified products can be obtained, which is preferable.

[Polystyrene and its modified substances]

Polystyrene and its modifications refer to compounds having polystyrene or a structure derived from polystyrene in the molecule.

唑啉共聚物(Epocros RPS-1005、RP-61均為日本觸媒公司製)、SEP(苯乙烯-伸乙基與丙烯共聚物：SEPTON 1020 KURARAY公司製)、SEPS(苯乙烯-伸乙基與丙烯-苯乙烯共聚物：SEPTON 2002、SEPTON 2004F、SEPTON 2005、SEPTON 2006、SEPTON 2063、SEPTON 2104均為KURARAY公司製)、SEEPS(苯乙烯-伸乙基/乙烯與丙烯-苯乙烯嵌段共聚物：SEPTON 4003、SEPTON 4044、SEPTON 4055、SEPTON 4077、SEPTON 4099均為KURARAY公司製)、SEBS(苯乙烯-伸乙基與丁烯-苯乙烯嵌段共聚物：SEPTON 8004、SEPTON 8006、SEPTON 8007L均為KURARAY公司製)、SEEPS-OH(在苯乙烯-伸乙基/乙烯與丙烯-苯乙烯嵌段共聚物之末端具有羥基的化合物：SEPTON HG252 KURARAY公司製)、SIS(苯乙烯-異戊二烯-苯乙烯嵌段共聚物：SEPTON 5125、SEPTON 5127均為KURARAY公司製)、氫化SIS(氫化苯乙烯-異戊二烯-苯乙烯嵌段共聚物：HYABRAR 7125F、HYABRAR 7311F均為KURARAY公司製)、SIBS(苯乙烯-異丁烯-苯乙烯嵌段共聚物：SIBSTAR073T、SIBSTAR102T、SIBSTAR103T(均為Kaneka公司製)、SEPTON V9827(KURARAY公司製))等，惟並非限於此等者。此外，此等係可使用1種，亦可使用複數種。聚苯乙烯及其改質物較佳為不具有不飽和鍵者，因而具有高耐熱性且難以氧化劣化。此外，聚苯乙烯及其改質物之重量平均分子量只要為10000以上則無特別限定，惟若過大，則與聚伸苯基醚化合物、重量平均分子量50至1000左右之低分子量成分、及重量平均分子量1000至5000左右之寡聚物成分的相溶性劣化，且難以確保混合及溶劑穩定性，從而較佳為10000至300000左右。 Examples of polystyrene and its modified products include: polystyrene, styrene and 2-isopropenyl-2-

Oxazoline copolymer (Epocros RPS-1005, RP-61 are both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylidene and propylene copolymer: SEPTON 1020 manufactured by KURARAY Co., Ltd.), SEPS (styrene-ethylidene) With propylene-styrene copolymer: SEPTON 2002, SEPTON 2004F, SEPTON 2005, SEPTON 2006, SEPTON 2063, SEPTON 2104 are all made by KURARAY Co., Ltd.), SEEPS (styrene-ethylidene/ethylene and propylene-styrene block copolymer) Materials: SEPTON 4003, SEPTON 4044, SEPTON 4055, SEPTON 4077, SEPTON 4099 are all manufactured by KURARAY Co., Ltd.), SEBS (styrene-ethylidene and butylene-styrene block copolymer: SEPTON 8004, SEPTON 8006, SEPTON 8007L All manufactured by KURARAY Co., Ltd.), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene-ethylidene/ethylene and propylene-styrene block copolymer: SEPTON HG252 manufactured by KURARAY Co., Ltd.), SIS (styrene-isopentyl) Diene-styrene block copolymer: SEPTON 5125, SEPTON 5127 are both manufactured by KURARAY Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: HYABRAR 7125F, HYABRAR 7311F are both manufactured by KURARAY Co., Ltd. (manufactured by Kaneka Co., Ltd.), SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all produced by Kaneka Co., Ltd.), SEPTON V9827 (manufactured by KURARAY Co., Ltd.)), etc., but are not limited to these. In addition, one type of these systems may be used, or a plurality of types may be used. Polystyrene and its modified products preferably do not have unsaturated bonds, so they have high heat resistance and are difficult to be oxidized and deteriorated. In addition, the weight average molecular weight of polystyrene and its modified products is not particularly limited as long as it is 10,000 or more. However, if it is too large, it will cause polyphenylene ether compounds, low molecular weight components with a weight average molecular weight of about 50 to 1,000, and weight average The compatibility of oligomer components with a molecular weight of about 1,000 to 5,000 deteriorates and it is difficult to ensure mixing and solvent stability, so the molecular weight is preferably about 10,000 to 300,000.

The content of polystyrene and its modified products is not particularly limited, but it is preferably 5 to 1000 parts by mass, and more preferably 10 to 750 parts by mass based on 100 parts by mass of the compound represented by formula (1). When the content of styrene and its modified products is in the above range, it is preferable because it not only has excellent heat resistance and the like, but also can obtain a cured product that fully exhibits the excellent dielectric properties of polystyrene and its modified products.

The curable resin composition of this embodiment is obtained by modulating the above-mentioned components in a predetermined ratio, pre-curing at 130 to 180°C for 30 to 500 seconds, and further post-curing at 150 to 200°C for 2 seconds. The hardening reaction proceeds sufficiently until 15 hours to obtain the hardened product of this embodiment. In addition, the components of the curable resin composition may be uniformly dispersed or dissolved in a solvent or the like, and then the solvent may be removed and then cured.

The preparation method of the curable resin composition of this embodiment is not particularly limited, as long as each component can be uniformly mixed or pre-polymerized. For example, in the presence or absence of a hardening accelerator or a polymerization initiator, in the presence or absence of a solvent, the maleimide compound represented by the aforementioned formula (1) and other The mixture of compounds is heated to perform prepolymerization. Similarly, an amine compound, a compound having an ethylenically unsaturated bond, a maleimide compound other than the maleimide compound represented by formula (1), a cyanate ester compound, and a polybutylene compound may be added. Dienes and their modifications, polystyrene and its modifications and other compounds, inorganic fillers, and other additives are prepolymerized. Regarding the mixing or prepolymerization of each component, if a solvent is not present, an extruder, a kneader, a roller press, etc. are used, and if a solvent is present, a reactor equipped with a stirring device, etc. is used.

Regarding the method of uniform mixing, a uniform resin composition is obtained by kneading at a temperature in the range of 50 to 100° C. using a kneader, a roller press, a planetary mixer, or the like. The obtained resin composition can also be pulverized and then molded into a cylindrical ingot shape using a molding machine such as a tablet press, or can be made into granular powder or a powdery molded body, or the composition can be melted and supported on the surface. The body is formed into a sheet with a thickness of 0.05 mm to 10 mm, thereby obtaining a curable resin composition molded body. The obtained molded body becomes non-sticky at 0 to 20°C, and its fluidity and hardening properties hardly decrease even if it is stored at -25 to 0°C for more than one week.

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

An organic solvent may be added to the curable resin composition of this embodiment to form a varnish-like composition (hereinafter referred to as varnish). If necessary, the curable resin composition of this embodiment is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethyl acetamide, In N-methylpyrrolidone and other solvents, make varnish, impregnate it in glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other base materials, and heat and dry the obtained prepreg. By performing body hot press molding, a cured product of the curable resin composition of this embodiment can be obtained. At this time, in the mixture of the curable resin composition of this embodiment and the solvent, the usage amount of the solvent is 10 to 70% by weight, preferably 15 to 70% by weight. In addition, if it is a liquid composition, a curable resin cured product containing carbon fibers can also be obtained directly by, for example, RTM method.

In addition, the curable composition of this embodiment can also be used as a modifier of a film-type composition. Specifically, it can be used to improve flexibility in the B-stage. Such a film-type resin composition is obtained by applying the curable resin composition of the present embodiment as the curable resin composition varnish on a release film, removing the solvent under heating, and then performing B-stage conversion. , and obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.

唑、聚醯亞胺及碳纖維等有機纖維，惟並非限定於此等。關於基材之形狀，並無特別限定，惟可列舉例如：織布、不織布、粗紗、短切原絲氈等。此外，關於織布的編織方法，已知有平紋織物、方平組織織物、斜紋織 物，可依據作為目的之用途和性能從此等習知者中適宜選擇使用。此外，較佳使用經開纖處理的織布或以矽烷偶合劑等進行表面處理的玻璃織布。關於基材之厚度，並無特別限定，惟較佳為0.01至0.4mm左右。此外，亦可藉由使強化纖維浸漬於前述清漆並進行加熱乾燥而獲得預浸體。 The curable resin composition of this embodiment can also be preformed by heating, melting, reducing the viscosity, and impregnating it with reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber. Dip body. 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 polyparaphenylene. Dimethylphenylenediamine (Kevlar (registered trademark), manufactured by DuPont), fully aromatic polyamide, polyester, polyparabenzo

Organic fibers such as azole, polyimide and carbon fiber, but are not limited to these. The shape of the base material is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, chopped strand mat, etc. In addition, as for the weaving method of the woven fabric, plain weave fabric, square weave fabric, and twill weave fabric are known, and those skilled in the art can select and use them appropriately according to the intended use and performance. In addition, it is preferable to use a fiber-opened woven fabric or a glass woven fabric surface-treated with a silane coupling agent or the like. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. In addition, a prepreg can also be obtained by impregnating reinforcing fibers in the varnish and drying them by heating.

In addition, the above-mentioned prepreg can also be used to produce a laminated board. The laminated board is not particularly limited as long as it contains one or more prepregs, and may have any other layers. The manufacturing method of the laminated board is not particularly limited, and generally known methods can be suitably used. For example, when molding metal foil-coated laminated boards, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used to laminate the above-mentioned prepregs and heat and press them. Get laminate boards. 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 pressing pressure is not particularly limited. However, 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 be unstable. In addition, if the pressure is too small, bubbles will occur and the adhesion between the laminates will deteriorate. , therefore, it is preferably 2.0 to 5.0MPa, and more preferably 2.5 to 4.0MPa. Since the laminated board of this embodiment has a layer made of metal foil, it can be suitably used as a metal foil-clad laminated board to be described later.

The above-mentioned prepreg is cut into a desired shape and laminated with copper foil or the like as necessary, and then the curable resin is added to the laminated product while applying pressure to the laminate using a press molding method, an autoclave molding method, a sheet winding molding method, or the like. By heating and hardening the composition, electrical and electronic laminates (printed wiring boards) and carbon fiber reinforced materials can be obtained.

The curable resin composition of this embodiment can also be made into a resin sheet. An example of a method for obtaining a resin sheet from the curable resin composition of this embodiment is to apply the curable resin composition on a support film (support) and then dry it to form a resin composition on the support film. object layer method. When the curable resin composition of this embodiment is used in a resin sheet, it is preferable that the film is softened under the temperature conditions of lamination (70°C to 140°C) in the vacuum lamination method, and is in contact with the circuit substrate. Lamination At the same time, it is important to demonstrate the fluidity (resin flow) that can be achieved by filling resin in via holes or through-holes existing in the circuit board, and to prepare each of the aforementioned components in a manner that exhibits such characteristics. In addition, the resulting resin sheet and circuit board (copper-clad laminate, etc.) do not exhibit locally different characteristic values due to phase separation, etc., and are designed to express certain performance at any location. Appearance uniformity is required.

Here, the diameter of the through hole of the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm. It is preferable that resin filling can be performed within this range. Moreover, when laminating both sides of a circuit board, it is desirable to fill approximately 1/2 of the through hole.

Specific methods for producing the resin sheet include: preparing a varnished resin composition by blending an organic solvent, coating the varnished resin composition on the surface of the support film (Y), and further heating the resin sheet. Or a method of drying the organic solvent by blowing hot air or the like to form the resin composition layer (X).

The organic solvent used here is preferably ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellulosine acetate, propylene glycol monomethyl ether acetate, and carboxylic acid. Acetates such as bitol acetate, carbitols such as cellulose and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N - Methylpyrrolidone, etc. In addition, it is preferably used in a ratio of 30 to 60% by mass of non-volatile matter.

In addition, the thickness of the resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit substrate is in the range of 5 to 70 μm, the thickness of the resin composition layer (X) is preferably in the range of 10 to 100 μm. In addition, in this embodiment, the aforementioned resin composition layer (X) can be protected by a protective film described later. By being protected by the protective film, dust adhesion and scratches on the surface of the resin composition layer can be prevented.

Examples of the support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET), and polyethylene naphthalate, and polycarbonates. Polyimide, release paper or metal foils such as copper foil and aluminum foil. In addition, the support film and protective film can be subjected to MAD treatment, corona treatment and demoulding treatment. The thickness of the supporting film is not particularly limited, but is 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) is peeled off after being laminated on the circuit board or after forming an insulating layer by heating and hardening. After the resin composition layer constituting the resin sheet is heated and hardened, if the support film (Y) is peeled off, dust and the like can be prevented from adhering during the hardening step. When peeling after hardening, the support film is subjected to a release treatment in advance.

Moreover, a multilayer printed circuit board can be manufactured from the resin sheet obtained as mentioned above. For example, when the resin composition layer (X) is protected by a protective film, after peeling off the resin composition layer (X), the resin composition layer (X) is directly contacted with the circuit substrate on one or both sides of the circuit substrate. Laminated by, for example, a vacuum lamination method. The laminating method can be a batch type or a continuous type using a roller press. In addition, if necessary, the resin sheet and the circuit board may be heated (preheated) as necessary before lamination. As for the lamination conditions, the pressing temperature (lamination temperature) is preferably set to 70 to 140°C, and the pressing pressure is preferably set to 1 to 11kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ), and it is preferable to laminate under reduced pressure of 20mmHg (26.7hPa) or less.

In addition, a semiconductor device can be manufactured using the curable resin composition of this embodiment. Examples of semiconductor devices include: DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (microcrystalline package), SOP (small outline package), TSOP (thin small outline package) ), TQFP (Thin Quad Flat Package), etc.

The curable resin composition and its cured product according to this embodiment can be used in a wide range of fields. Specifically, it can be used in various applications such as molding materials, adhesives, composite materials, and coatings. Since the cured product of the curable resin composition described in this embodiment shows excellent heat resistance and dielectric properties, it is preferably used as a sealing material for semiconductor elements, a sealing material for liquid crystal display elements, and a sealing material for organic EL elements. , composite materials for electrical and electronic parts such as laminated boards (printed wiring boards, BGA substrates, assembly substrates, etc.) and lightweight high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.

[Example]

Next, the present invention will be described in more detail based on examples. Hereinafter, parts refer to parts by mass unless otherwise stated. In addition, the present invention is not limited to these embodiments.

Various analysis methods used in the Examples are described below.

‧GPC (gel permeation chromatography) analysis

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

GPC: Online degassing device (DGU-20A3R), binary pipetting device (LC-20AD), automatic sampler (SIL-20AHT), differential refractive index detector (RID-20A), column oven (CTO- 20A), system controller (CBM-20A) (both manufactured by Shimadzu Corporation)

Pipe string: Shodex KF-603×1, KF-602.5×1, KF-602×1, KF-601×1 (all manufactured by Showa Denko Co., Ltd.)

Protection column: Shodex KF-G 4A (manufactured by Showa Denko Co., Ltd.)

Combined eluents: tetrahydrofuran

Flow rate: 1.5ml/min.

Tube string temperature: 40℃

Detection: RI (differential refraction detector)

‧ ¹ H-NMR analysis

Equipment: Nuclear Magnetic Resonance Equipment (JNM-ECS400) manufactured by Japan Electronics Co., Ltd.

[Example 1]

In a flask equipped with a thermometer, a cooling tube, a stirrer, and a Dean-Stark device, 24.3 parts of 2,6-dimethylaniline, α,α,α',α'-tetrahydrofuran were added. 136 parts of methyl-1,3-benzenedimethanol, 100 parts of toluene, and 35 parts of activated clay were reacted at an internal temperature of 110 to 135°C for 1.5 hours while removing the water produced by azeotropic dehydration. Thereafter, while extracting toluene, the internal temperature was raised to 210°C, and the reaction was carried out for 4 hours. After cooling, the extracted toluene is returned to the system, and 200 parts of toluene are added. The activated clay was removed by filtration, and a toluene solution (T-1) containing an amine compound represented by the following formula (6) was obtained. The GPC chart of the obtained amine compound is shown in Figure 1 .

Then, 100 parts of toluene, 29.4 parts of maleic anhydride, and 5.4 parts of methanesulfonic acid were added to a flask equipped with a thermometer, a cooling tube, a stirrer, and a Dean-Stark device, while maintaining the internal temperature at 110°C. , while adding T-1 dropwise for 4 hours. Furthermore, the polymerization reaction of the olefin part of the amine represented by the following formula (6) and the maleide imidization reaction of the amine group were performed at 110° C. for 9 hours. After leaving to cool, 200 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. The solvent was distilled off under heating and reduced pressure, thereby obtaining 133 parts of a maleimide compound (M-1) represented by the following formula (7) as a brown solid resin. The GPC chart of the obtained maleimide compound is shown in Figure 2 . The number average molecular weight (Mn) is 2082, and the weight average molecular weight (Mw) is 3169. In addition, the ¹ H-NMR chart (heavy chloroform) of the obtained maleimide compound is shown in FIG. 3 . A signal originating from the maleimide group was observed at 6.85 ppm in the ¹ H-NMR chart.

[Example 2]

In a flask equipped with a thermometer, cooling tube, stirrer, and Dean Stark device, 35.4 parts of 2,6-diisopropylaniline and α,α,α',α'-tetramethyl-1 were fed , 136 parts of 3-benzenedimethanol, 100 parts of toluene, and 35 parts of activated clay were reacted at an internal temperature of 110 to 135°C for 2 hours while removing the water produced by azeotropic dehydration. Thereafter, while extracting toluene, the internal temperature was raised to 210°C, and the reaction was carried out for 9 hours. After cooling, the extracted toluene is returned to the system, and 200 parts of toluene are added. The activated clay was removed by filtration, and a toluene solution (T-2) containing an amine compound represented by the following formula (8) was obtained. The GPC chart of the obtained amine compound is shown in Figure 4 .

Then, 100 parts of toluene, 29.4 parts of maleic anhydride, and 5.4 parts of methanesulfonic acid were added to a flask equipped with a thermometer, a cooling tube, a stirrer, and a Dean-Stark device, while maintaining the internal temperature at 110°C. ℃, while adding T-2 dropwise for 2 hours. Furthermore, the polymerization reaction of the olefin part of the amine compound represented by the following formula (8) and the maleide imidization reaction of the amine group were performed at 110° C. for 10 hours. After leaving to cool, 200 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. The solvent was distilled off under heating and reduced pressure, thereby obtaining 125 parts of a maleimide compound (M-2) represented by the following formula (9) as a brown solid resin. The GPC chart of the obtained maleimide compound is shown in Figure 5 . The number average molecular weight (Mn) is 2007, and the weight average molecular weight (Mw) is 3301. In addition, the ¹ H-NMR chart (heavy chloroform) of the obtained maleimide compound is shown in FIG. 6 . A signal originating from the maleimide group was observed at 6.85 ppm in the ¹ H-NMR chart.

[Synthesis example 1]

In a flask equipped with a thermometer, cooling tube, stirrer, and Dean Stark apparatus, 48.5 parts of 2,6-dimethylaniline and α,α,α',α'-tetramethyl-1,3 are fed - 155.4 parts of benzenedimethanol, 100 parts of toluene, and 30.6 parts of activated clay, while removing toluene and the generated water by azeotropic dehydration, raise the internal temperature to 210°C for 2 hours, and react for 3 hours (the GPC chart is shown in Figure 7). After cooling the internal temperature to 120°C, 145.4 parts of 2,6-dimethylaniline was added and the reaction was carried out at 220°C for 3 hours. After cooling, the extracted toluene is returned to the system, and 200 parts of toluene are added. The activated clay was removed by filtration, and the solvent and excess 2,6-dimethylaniline were distilled off to obtain 207 parts of the amine compound (A-1) represented by the following formula (10) as a brown solid resin. (Amine equivalent: 272.7g/eq.). The GPC chart of the obtained amine compound is shown in Figure 7 . The number average molecular weight (Mn) is 1048, and the weight average molecular weight (Mw) is 1252.

[Synthesis example 2]

In a flask equipped with a thermometer, cooling tube, stirrer, and Dean Stark apparatus, add 50 parts of toluene, 53.9 parts of maleic anhydride, and 2 parts of methanesulfonic acid, and drip for 1 hour while maintaining the reflux state. Add the toluene and N-methylpyrrolidone (NMP) solution of A-1 (A-1: 100 parts, toluene: 75 parts, NMP 25 parts). The maleic acid imidization reaction of the amine group was carried out under reflux conditions for 2 hours. After leaving to cool, 100 parts of toluene was added, and the organic layer was washed 5 times with 100 parts of water. The solvent was distilled off under heating and reduced pressure to obtain 117 parts of a maleimide compound (M-3) represented by the following formula (11) as a brown solid resin. The GPC chart of the obtained maleimide compound is shown in FIG. 8 . The number average molecular weight (Mn) is 1353, and the weight average molecular weight (Mw) is 1562.

[Examples 3 to 6, Comparative Example 1]

Each of the maleimide compounds (M-1, M-2, M-3) obtained in Examples 1 to 2 and Synthesis Example 2 and the thermal radical initiator DCP (dicumyl peroxide, (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed at the ratios shown in Table 1 and Table 2 respectively, and then vacuum press-molded while clamped with mirror copper foil (T4X: manufactured by Fukuda Metal Copper Foil Co., Ltd.), and cured at 220°C for 2 hours. . At this time, as a spacer, a buffer paper with a thickness of 250 μm was used in which the center was hollowed out by 150 mm in length and width. During the evaluation, if necessary, use a laser cutting machine to cut test pieces of the desired size and perform evaluation. The evaluation results are shown in Table 1 and Table 2.

<Dielectric constant test, dielectric tangent test>

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

[Table 1]

<Heat resistance: Differential scanning calorimetry (DSC)>

The glass transition point Tg of the samples of Examples 5 and 6 was measured using a differential scanning thermal analyzer.

Differential scanning thermal analyzer: DSC6220 (manufactured by SII Nanotechnology Co., Ltd.)

Measuring temperature range: 30 to 330℃

Heating rate: 10℃/min

Ambient gas: nitrogen (30mL/min)

Sample volume: 5mg

Tg: Set the inflection point of the DSC chart to Tg.

[Table 2]

Based on the results in Table 1 and Table 2, it was confirmed that the curable resin composition of the present invention has excellent dielectric properties and heat resistance.

This patent application claims priority based on Japanese Patent Application No. 2022-052578 filed on March 28, 2022.

[Industrial Applicability]

The curable resin composition containing the maleimide compound of the present invention and the cured product obtained by curing thereof are suitable for use in electrical and electronic components such as semiconductor sealing materials, printed wiring boards, and assembly laminates.

Claims (8)

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

Wherein, in the formula (1), there are multiple R's that exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; X is represented by the following formula (2); m is from 0 to 4 Integer, n is a repeated number, the average n _ave of n conforms to 1≦n _ave ≦20;

In formula (2), a plurality of R exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; p represents an integer from 0 to 4, q represents an integer from 0 to 3; r is a repeat. Number, the average r _ave of r is consistent with 1≦r _ave ≦20; * indicates the bonding position with the aromatic ring of the aforementioned formula (1). A maleimide compound represented by the following formula (3),

Among _them , in formula (3) _,

In formula (4), a plurality of R exist independently and represent a hydrocarbon group with a carbon number of 1 to 5; p represents an integer from 0 to 4, r is the repeat number, and the average r _ave of r conforms to 1.1≦r _ave ≦20; * indicates the bonding position with the aromatic ring of the compound of formula (3). The maleimide compound according to claim 2, wherein in the formula (4), p is 2, and the substitution position of R is ortho position with respect to the maleimide group. 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 contains a radical polymerization initiator. A hardened product obtained by hardening the curable resin composition described in claim 4 or 5. An amine compound represented by the following formula (5),

Wherein, in formula (5), there are multiple R's that exist independently and represent a hydrocarbon group or a halogenated alkyl group having 1 to 10 carbon atoms; p represents an integer from 0 to 4, q represents an integer from 0 to 3; r is the number of repetitions, and the average r _ave of r conforms to 1≦r _ave ≦20. A reactant between the amine compound described in claim 7 and maleic anhydride.

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