TW202440664A - Compound, curable resin composition and cured products thereof - Google Patents

Abstract

The present invention provides a compound having excellent low dielectric properties, a curable resin composition, and cured products thereof.

Provided is a compound obtained by reacting an acid-modified hydrogenated thermoplastic styrenic elastomer (AH-AB) with allylamine or allylamine hydrochloride. The aforesaid acid-modified hydrogenated thermoplastic styrenic elastomer (AH-AB) is an acid-modified product of a hydrogenated product (H-AB) of a block copolymer consisting of a polymer block unit (A) that contains a styrene monomer and a polymer block unit (B) that contains a conjugated diene compound.

Description

Compounds, hardening resin compositions and hardened products thereof

The present invention relates to a compound with a specific structure, a curable resin composition and its cured product, which is suitable for use in semiconductor sealing materials, printed wiring boards, build-up laminates and other electrical and electronic parts, carbon fiber reinforced plastics, glass fiber reinforced plastics and other lightweight and high-strength materials, and 3D printing applications.

In recent years, the application fields of multilayer boards equipped with electrical and electronic components have expanded, and the required characteristics have become wider and more advanced. In the past, semiconductor chips were mainly mounted on metal wire frames, but semiconductor chips with higher processing capabilities such as central processing units (hereinafter referred to as CPUs) are mostly mounted on multilayer boards made of polymer materials.

The fifth generation communication system "5G" which is currently under accelerated development is expected to develop greater capacity and high-speed communication. With the increase in the frequency used in 5G, it is important to reduce transmission loss to achieve high-speed communication using high frequency, and substrate materials require lower dielectric properties (low dielectric constant and low loss tangent). The transmission loss generated on the printed circuit board comes from conductor loss and dielectric loss. As described in non-patent document 1, the dielectric loss _αD is proportional to the square root of the relative dielectric constant _εγ of the dielectric and the loss tangent tanδ. Therefore, if you want to reduce the dielectric loss, it is more effective to reduce the loss tangent than to reduce the relative dielectric constant. Low dielectric materials include thermoplastic materials such as PTFE (polytetrafluoroethylene) and LCP (liquid crystal polymer), but they lack moldability compared to thermosetting resins. In view of this, it is required to develop thermosetting resins with excellent low dielectric properties.

In view of this, a thermosetting resin with excellent low dielectric properties is discussed. For example, Patent Document 1 proposes a thermosetting resin composition, which includes an imide compound having a maleimide group and a phenol aralkyl resin having an aliphatic unsaturated bond. However, on the other hand, phenolic hydroxyl groups that do not participate in the reaction will remain during the curing reaction, so it is difficult to say that the electrical properties are sufficient. In addition, Patent Document 2 discloses an allyl ether modified biphenyl aralkyl phenol formaldehyde varnish resin in which an allyl group is added to a phenolic hydroxyl group. However, allyl ether-modified biphenyl phenolic varnish resin will produce Clayssen rearrangement at 190°C, and will generate phenolic hydroxyl groups that do not participate in the curing reaction at 200°C, the molding temperature of general substrates, so it cannot meet the electrical properties.

[Prior Art Literature]

[Non-patent literature]

Non-patent document 1: "Causes of signal loss in high-speed signal transmission on printed circuit boards", 29th Spring Lecture Meeting of the Japan Institute of Electronics Packaging, Session ID: 16P1-17, 2015.

[Patent Literature]

Patent document 1: Japanese Patent Publication No. 04-359911.

Patent document 2: International Publication No. 2016/002704.

This invention was developed in view of this situation, and its purpose is to provide a compound with excellent low dielectric properties, a curable resin composition and its cured product.

That is, the present invention relates to the following [1] to [11]. In addition, in this case, "(value 1) to (value 2)" includes upper and lower limits.

[1] A compound obtained by reacting an acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) with allylamine or allylamine hydrochloride, wherein the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) is an acid-modified product of a hydrogenated product (H-AB) of a block copolymer, wherein the block copolymer is composed of a block unit (A) of a polymer containing a styrene monomer and a block unit (B) of a polymer containing a conjugated diene compound.

[2] The compound as described in the above item [1], wherein the block unit (A) of the polymer containing styrene monomers is a structure represented by the following formula (a).

In formula (1), _R1 and _R2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, p is 1 to 5, and q is an average value of repeated numbers and represents a real number from 1 to 10,000.

[3] The compound as described in item [1] above, wherein the block unit (B) of the polymer comprising a conjugated diene compound is obtained by polymerizing at least one diene compound selected from 1,3-butadiene, isoprene, chalcone, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene.

[4] The compound as described in the above item [1], wherein the hydrogenated product of the block copolymer (H-AB) is a compound represented by the following formula (1).

In formula (1), _R1 and _R2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, p is 1 to 5, and j, k, l, m, and n are average values of repetition numbers and represent real numbers from 1 to 10000. The order of the repetition units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern may be any of alternating, block, and random.

[5] The compound as described in the above item [1], wherein the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) is a compound represented by the following formula (2).

In formula (2), _R1 and _R2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, p is 1 to 5, and j, k, l, m, and n are average values of repetition numbers and represent real numbers from 1 to 10000. The order of the repetition units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern may be any of alternating, block, and random.

[6] A compound represented by the following formula (3).

(In formula (3), j, k, l, m, and n are average values of the repetition numbers and represent real numbers from 1 to 10,000. The order of the repetition units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random.)

[7] A hardening resin composition comprising a compound as described in any one of the above items [1] to [6].

[8] The hardening resin composition as described in the above item [7] further contains a polymerization initiator.

[9] The curable resin composition as described in the preceding item [7] or [8], further comprising at least one of a maleimide compound, a polyphenylene ether compound, a compound having an ethylenic unsaturated bond, a cyanate resin, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products.

[10] A hardened material, which is a hardened material of a compound as described in any one of the preceding items [1] to [6].

[11] A hardened product, which is a hardened product of the hardening resin composition as described in any one of the preceding items [7] to [9].

According to the present invention, a compound with excellent low dielectric properties, a curable resin composition, and the cured products thereof can be provided.

Figure 1 shows the GPC chart of Synthesis Example 1.

The compound of the present invention is obtained by reacting an acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) with allylamine or allylamine hydrochloride. The acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) is an acid-modified product of a hydrogenated block copolymer (H-AB). The block copolymer is composed of a block unit (A) of a polymer containing a styrene monomer and a block unit (B) of a polymer containing a conjugated diene compound.

The block unit (A) of the polymer containing styrene monomers is preferably a structure represented by the following formula (a).

_R1 and _R2 are each preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, particularly preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom. If the carbon number is greater than 5, there is a risk that the loss tangent will deteriorate due to molecular vibration and that the heat resistance will decrease. p is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. q is an average value of repeated numbers and represents a real number of 1 to 10,000, and q is preferably 1 to 7,500, more preferably 1 to 5,000, and even more preferably 1 to 3,000.

The block unit (B) of the polymer containing a conjugated diene compound is obtained by polymerizing at least one diene compound selected from chain conjugated dienes such as 1,3-butadiene, isoprene, acathene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. From the perspective of the availability of raw materials, the chain conjugated dienes are preferably 1,3-butadiene, isoprene, and acathene, more preferably 1,3-butadiene and isoprene, and most preferably 1,3-butadiene.

Any material known as a hydrogenated block copolymer (H-AB) can be used, preferably a compound represented by the following formula (1).

In formula (1), the values and preferred ranges of R ₁ , R ₂ , and p are the same as those of formula (a). j, k, l, m, and n are average values of repetition numbers and represent real numbers ranging from 1 to 10,000, preferably from 1 to 9,000, and more preferably from 1 to 8,000. The order of the repetition units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern may be any of alternating, block, and random.

Particularly preferred is the compound represented by the following formula (1-1).

In formula (1-1), the values and preferred ranges of j, k, l, m, and n are the same as those in the aforementioned formula (1). The order of the repeated units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random.

The best embodiment of the hydrogenated block copolymer (H-AB) is when hydrogenated styrene/butadiene/styrene block copolymer (SEBS) is used.

The compound represented by the above formula (1) has no polar group and no unsaturated bond derived from aliphatic hydrocarbons. Therefore, it is not easy to oxidize even if it is exposed to the semiconductor operation guarantee temperature of 125°C or above for a long time. The oxygen contained in the polar group is not easy to enter the skeleton. Therefore, the dielectric property deterioration after high temperature placement test can be reduced, and the low water absorption property is also excellent.

The acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) may be any known material, preferably a compound represented by the following formula (2).

The values and preferred ranges of R ₁ , R ₂ , p, j, k, l, m, and n in formula (2) are the same as those in formula (1). The order of the repeating units in parentheses with k and l, or j and m and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random.

Particularly preferred is the compound represented by the following formula (2-1).

The values and preferred ranges of j, k, l, m, and n in formula (2-1) are the same as those in formula (1). The order of the repeated units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random.

The best embodiment of the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) is the case of using acid-modified hydrogenated styrene/butadiene/styrene block copolymer (SEBS).

The compound represented by the aforementioned formula (2) is obtained by reacting the compound represented by the aforementioned formula (1) with maleic anhydride in the presence of a free radical polymerization initiator, or reacting the compound represented by the aforementioned formula (1) with maleic acid in the presence of a free radical polymerization initiator and then dehydrating the reaction.

The compound represented by the aforementioned formula (2-1) is obtained by reacting the compound represented by the aforementioned formula (1-1) with maleic anhydride in the presence of a free radical polymerization initiator, or reacting the compound represented by the aforementioned formula (1-1) with maleic acid in the presence of a free radical polymerization initiator and then dehydrating the reaction.

From the perspective of high-frequency characteristics (low dielectric constant, low loss tangent), adhesion to conductors, heat resistance, glass transition temperature and thermal expansion coefficient, the content of structural units derived from styrene in the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) (hereinafter referred to as styrene content) can be 5 to 80% by mass, 5 to 70% by mass, 10 to 70% by mass, or 10 to 50% by mass. The melt flow rate (MFR) of the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) is not particularly limited and can be 0.1 to 20 g/10 min or 0.5 to 15 g/10 min under the measurement conditions of 230°C and a load of 2.16 kgf (21.2 N).

Commercially available products of acid-modified hydrogenated thermoplastic styrene elastomers (AH-AB) include, for example, Tuftec (registered trademark) M series manufactured by Asahi Kasei Corporation.

The preferred structure of the compound of the present invention obtained by reacting an acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) with allylamine or allylamine hydrochloride is shown in the following formula (3).

The values and preferred ranges of R ₁ , R ₂ , p, j, k, l, m, and n in formula (3) are the same as those in formula (1). The order of the repeating units in parentheses with k and l, or j and m and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random.

Particularly preferred is the compound represented by the following formula (3-1).

The values and preferred ranges of j, k, l, m, and n in formula (3-1) are the same as those in formula (1). The order of the repeated units in parentheses with k and l, or j and m and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random.

The best embodiment of the compound of the present invention is the case of using a compound having a structure derived from acid-modified hydrogenated styrene/butadiene/styrene block copolymer (SEBS).

The reaction of the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) with allylamine or allylamine hydrochloride can be carried out by any known imidization reaction method, for example, by reacting allylamine or allylamine hydrochloride with the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) in a water-insoluble aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, etc., while removing the generated water from the system by azeotropic distillation. The imidization catalyst can be an alkaline catalyst such as triethylamine, or an acid catalyst such as activated clay, p-toluenesulfonic acid, methanesulfonic acid, hydrochloric acid, etc. For the purpose of dissolving the acylamine and promoting the imidization step, a non-protonic polar solvent such as N-methyl-2-pyrrolidone or N,N-dimethylformamide can be used in combination. Relative to 1 mol of the anhydride structure, the amount of allylamine or allylamine hydrochloride is preferably 0.5 to 1.5 mol, more preferably 0.8 to 1.2 mol, and most preferably 0.9 to 1.1 mol. When the above range is exceeded, there is a risk that the dielectric properties will deteriorate due to the polar groups of the residual raw materials. The above reaction is carried out at 80 to 200°C, preferably at 100 to 180°C for 0.5 to 20 hours.

The number average molecular weight of the compound of the present invention measured by gel permeation chromatography (GPC) is preferably 10,000 or more and less than 1,000,000, more preferably 20,000 or more and less than 500,000, and even more preferably 30,000 or more and less than 250,000. If it is less than 10,000, the heat resistance in the solder reflow step may be impaired. If it is more than 1,000,000, the solvent solubility may be impaired or it may not be fully compatible with other thermosetting resin components.

The curable resin composition of the present invention can be mixed with various materials shown below in addition to the compound of the present invention.

[Polymerization initiator]

The curable resin composition of the present invention can also be cured by adding a polymerization initiator. A polymerization initiator refers to a compound that can polymerize olefin functional groups such as ethylene unsaturated bonds, and can include olefin substitution polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, free radical polymerization initiators, etc. Among them, it is preferred to use a free radical polymerization initiator with curability and appropriate stability. A free radical polymerization initiator refers to a compound that generates free radicals and starts a chain polymerization reaction by irradiating ultraviolet rays or visible light or heating. The free radical polymerization initiators that can be used include organic peroxides, azo compounds, benzopinacols, etc. From the perspective of controlling the curing temperature or inhibiting gas release and having less impact on the electrical properties of the decomposed product, it is better to use organic peroxides.

The organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as diisopropylbenzene peroxide and 1,3-bis-(tert-butylperoxyisopropyl)-benzene, peroxyketal peroxides such as tert-butyl peroxybenzoate and 1,1-di-tert-butylperoxycyclohexane, α-isopropyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3-methyl-1-butyl ... Alkyl peroxyesters such as tripentyl peroxide, t-butyl peroxide 2-ethylhexanoate, t-pentyl peroxide 3,5,5-trimethylhexanoate, t-butyl peroxide 3,5,5-trimethylhexanoate, and t-pentyl peroxide benzoate; peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyisopropylcarbonate, and 1,6-bis(t-butylperoxycarbonyloxy)hexane; t-butyl hydroperoxide, isopropyl hydroperoxide, t-butyl peroxyoctanoate, and lauryl peroxide, but not limited to these. These may be used alone or in combination. Among the above-mentioned organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketal peroxides, alkyl peroxyesters, peroxycarbonates, etc. are preferred, and dialkyl peroxides are more preferred.

The above-mentioned azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), etc. Moreover, these compounds may be used alone or in combination.

The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, in 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 parts by mass, there is a risk that the molecular weight cannot be fully extended during the polymerization reaction. If it is more than 5 parts by mass, there is a risk that the dielectric constant, loss tangent and other dielectric properties will be damaged.

[Hardening accelerator]

The curable resin composition of the present invention can also improve the curability by adding a curing accelerator. The curing accelerator is preferably a cationic curing accelerator that generates anions by irradiating ultraviolet rays, visible light or heating to promote the curing reaction, or a cationic curing accelerator that generates cations by irradiating ultraviolet rays, visible light or heating to promote the curing reaction.

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-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, preferably 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene. Other examples include phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethylammonium hydroxide and other quaternary ammonium salts, but are not limited to these. Moreover, these may be used alone or in combination of multiple types.

Cationic hardening accelerators include, for example, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the relative ions of the quaternary salts are halogens, organic acid ions, hydroxide ions, etc., although not specifically specified, organic acid ions and hydroxide ions are particularly preferred), tin octanoate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristic acid), zinc phosphates (octyl zinc phosphate, stearyl zinc phosphate) and other transition metal compounds (transition metal salts), but are not limited to these. Moreover, these can be used alone or in combination.

The amount of curing accelerator blended in 100 parts by mass of the curable resin composition can be 0.01 to 5.0 parts by mass as needed.

[Inorganic fillers]

The curable resin composition of the present invention 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, zirconium dioxide, aluminum nitride, graphite, olivine, steatite, spinel, andalusite, titanium dioxide, talc, clay, ferric oxide asbestos, glass powder and other powders, or inorganic fillers formed into spherical or crushed shapes, but are not limited to these. Moreover, these may be used alone or in combination.

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

[Polymerization inhibitor]

The curable resin composition of the present invention may contain a polymerization inhibitor. By containing a polymerization inhibitor, the storage stability can be improved and the reaction starting temperature can be controlled. By controlling the reaction starting temperature, the fluidity can be easily ensured, and the B stage of prepreg can be made easier without damaging the impregnation of glass cloth, etc. If the polymerization reaction is too advanced during prepreg, it is easy to cause adverse conditions such as difficulty in lamination in the lamination step.

The polymerization inhibitor can be added during the synthesis of the compound of the present invention, or can be added after the synthesis. The amount of the polymerization inhibitor used is 0.008 to 1 part by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the compound of the present invention.

Examples of polymerization inhibitors include phenolic, sulfuric, phosphorus, hindered amine, nitroso, and nitroxide free radicals. In addition, polymerization inhibitors may be used alone or in combination. Among these, phenolic, hindered amine, nitroso, and nitroxide free radicals are preferred in the present invention.

、2,4-雙[(辛基硫基)甲基]-鄰甲酚等單酚類；2,2’-亞甲基雙(4-甲基-6-第三丁基酚)、2,2’-亞甲基雙(4-乙基-6-第三丁基酚)、4,4’-硫雙(3-甲基-6-第三丁基酚)、4,4’-亞丁基雙(3-甲基-6-第三丁基酚)、三乙二醇-雙[3-(3-第三丁基-5-甲基-4-羥基苯基)丙酸酯]、1,6-己二醇-雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、N,N’-六亞甲基雙(3,5-二第三丁基-4-羥基-氫化桂皮醯胺)、2,2-硫-二伸乙基雙[3-(3,5-二第三丁基-4-羥基苯基)丙酸酯]、3,5-二第三丁基-4-羥基苄基磷酸二乙酯、3,9-雙[1,1-二甲基-2-{β-(3-第三丁基-4-羥基-5-甲基苯基)丙醯基氧基}乙基]2,4,8,10-四氧雜螺[5,5]十一烷、雙(3,5-二第三丁基-4-羥基苄基磺酸乙酯)鈣等雙酚類；1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二第三丁基-4-羥基苄基)苯、四-[亞甲基-3- (3’,5’-二第三丁基-4’-羥基苯基)丙酸酯]甲烷、雙[3,3’-雙-(4’-羥基-3’-第三丁基苯基)丁酸]二醇酯、三-(3,5-二第三丁基-4-羥基苄基)-三聚異氰酸酯、1,3,5-三(3’,5’-二第三丁基-4’-羥基苄基)-S-三

-2,4,6-(1H,3H,5H)三酮、生育酚等高分子型苯酚類等，但並不限定於該等。 The above-mentioned phenolic polymerization inhibitors include, for example, 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-tris(2-hydroxy-3,5-di-tert-butyl)propionate, and 1,3,5-tris(2-hydroxy-3,5-di-tert-butyl)propionate.

, 2,4-bis[(octylthio)methyl]-o-cresol and other monophenols; 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 2,2-thio- Bisphenols such as diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphate, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-tert-butyl-4-hydroxybenzylsulfonate) calcium; 1,1,3-tri(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tri(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3- (3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl) butyrate] diol, tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanate, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-tri

-2,4,6-(1H,3H,5H)trione, high molecular weight phenols such as tocopherol, etc., but are not limited to them.

The above-mentioned sulfur-based polymerization inhibitors include, for example, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, etc., but are not limited to them.

Examples of the phosphorus-based polymerization inhibitor include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl neopentyltritol phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl)phosphite, cyclic neopentanetetraylbis(2,4-di-tert-butylphenyl)phosphite, bis[2-tert-butyl- Phosphites such as 6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrophosphite, 9,10-dihydro-9-oxo-10-phosphophanthenanthrene-10-oxide, 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxo-10-phosphophanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxo-10-phosphophanthrene-10-oxide, and the like, but are not limited thereto.

Examples of the hindered amine polymerization inhibitor include ADK STAB LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, ADK STAB LA-82, ADK STAB LA-81, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK STAB LA-52, Chimassorb2020FDL, Chimassorb944FDL, Chimassorb944LD, Tinuvin622SF, TinuvinPA144, Tinuvin765, Tinuvin770DF, TinuvinXT55FB, Tinuvin111FDL, Tinuvin783FDL, Tinuvin791FB, etc., but not limited to them.

The above-mentioned nitroso polymerization inhibitors include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salt of N-nitrosophenylhydroxylamine (copper iron), etc. Among them, ammonium salt of N-nitrosophenylhydroxylamine (copper iron) is preferred.

The above-mentioned nitroxide free radical polymerization inhibitor can be exemplified by di-tert-butyl nitroxide free radical, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl, etc., but is not limited to them.

[Flame retardant]

The curable resin composition of the present invention can use a flame retardant. Examples of the flame retardant include halogen flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), phosphorus flame retardants, etc. From the perspective of achieving halogen-free flame retardancy, phosphorus flame retardants are preferred. The above-mentioned phosphorus flame retardants can be reactive or additive. Specific examples include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(thio)phosphate, cresyl diphenyl phosphate, cresyl-2,6-dithiophosphate, 1,3-phenylenebis(dithiophosphate), 1,4-phenylenebis(dithiophosphate), 4,4'-biphenyl(dithiophosphate), and other phosphates, phosphanes such as 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl)-10H-9-oxo-10-phosphaphenanthrene-10-oxide, and phosphorus-containing epoxides obtained by reacting epoxy resins with active hydrogen of the above-mentioned phosphanes, red phosphorus, etc., but are not limited thereto. Moreover, these may be used alone or in combination of a plurality of them. Among the above-mentioned exemplified substances, preferred are phosphates, phosphanes or phosphorus-containing epoxides, and particularly preferred are 1,3-phenylenebis(dithiophosphate), 1,4-phenylenebis(dithiophosphate), 4,4'-biphenylene(dithiophosphate) or phosphorus-containing epoxides.

The content of the flame retardant is preferably in the range of 0.1 to 0.6 parts by mass in 100 parts by mass of the curable resin composition. If it is less than 0.1 parts by mass, there is a risk of insufficient flame retardancy, and if it exceeds 0.6 parts by mass, there is a risk of adversely affecting the hygroscopicity and dielectric properties of the cured product.

[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)丁胺之反應物、琥珀酸二甲酯-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]丁基丙二酸酯、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、2-(3,5-二第三丁基-4-羥基苄基)-2-正丁基丙二酸雙(1,2,2,6,6-五甲基-4-哌啶基)等，但並不限定於該等。又，該等可使用1種或併用複數種。 The curable resin composition of the present invention can use a light stabilizer. The light stabilizer is preferably a hindered amine light stabilizer, and HALS is particularly preferred. HALS can be exemplified by dibutylamine, 1,3,5-triazine,

． N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine reactants, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine reactants, 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)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl The present invention also includes, but is not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidinyl), and the like. Moreover, these may be used alone or in combination of a plurality of them.

The content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass in 100 parts by mass of the curable resin composition. If it is less than 0.001 parts by mass, the light stabilization effect may not be fully demonstrated. If it exceeds 0.1 parts by mass, the moisture absorption and dielectric properties of the cured product may be adversely affected.

[Adhesive resin]

The curable resin composition of the present invention can use an adhesive resin. Examples of adhesive resins include butyraldehyde resins, acetal resins, acrylic resins, epoxy-resin resins, NBR-phenol resins, epoxy-NBR resins, silicone resins, etc., but are not limited to them. Moreover, these resins can be used alone or in combination.

The amount of adhesive resin blended is preferably within the range that does not damage the flame retardancy and heat resistance of the cured product. It is preferably 0.05 to 50 parts by mass in 100 parts by mass of the curable resin composition, and more preferably 0.05 to 20 parts by mass.

[Additives]

The curable resin composition of the present invention can use additives. Examples of additives include modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, mold release agents, carbon black, phthalocyanine blue, phthalocyanine green and other coloring agents.

The amount of the additive blended is preferably less than 1 part by mass, and more preferably less than 0.7 parts by mass, relative to 100 parts by mass of the curable resin composition.

The curable resin composition of the present invention may further use epoxy resins, active ester compounds, phenol resins, polyphenylene ether compounds, amine resins, compounds having ethylenic unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate resins, polyimide resins, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products, etc. These may be used alone or in combination. Among these compounds, maleimide compounds, polyphenylene ether compounds, compounds having ethylenic unsaturated bonds, cyanate resins, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products are preferably used in terms of the balance of heat resistance, adhesion, and dielectric properties. By containing these compounds, the brittleness of the hardened material can be improved and the adhesion to metal can be increased, and the cracking of the package during solder reflow or hot and cold cycle reliability tests can be suppressed. The total amount of the above compounds used is preferably 10 times or less by mass, more preferably 5 times or less by mass, and particularly preferably 3 times or less by mass relative to the compound of the present invention when not specifically stated. In addition, the preferred lower limit is 0.1 times or more by mass, more preferably 0.25 times or more by mass, and even more preferably 0.5 times or more by mass. By being within the above range, the effect of the low dielectric properties of the compound of the present invention can be exerted, and the effects of each added compound can be added. The following examples can be used for these components.

[Epoxy resin]

The following are examples of preferred epoxy resins, but are not limited to them. In addition, the epoxy resin can be liquid or solid, and one or more types can be used.

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, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidyl amine type epoxy resin, and epoxy resins having a butadiene structure. Specific examples include "RE310S", "RE410S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER828EL", "825", "828EL" (All of the above are bisphenol A epoxy resins made by Mitsubishi Chemical), "jE807", "1750" (All of the above are bisphenol F epoxy resins made by Mitsubishi Chemical), "jER152" (Mitsubishi Chemical, phenol novolac epoxy resin), "630", "630LSD" (All of the above are propylene oxide epoxy resins made by Mitsubishi Chemical), "ZX1059" (Mixture of bisphenol A epoxy resin and bisphenol F epoxy resin made by Nippon Steel Sumitomo Chemical Co., Ltd.), "EX-721" (Nagase ChemteX, epoxy ester type epoxy resin), "Celloxide 2021P" (Daicel, epoxy resin with ester skeleton), "PB-3600" (Daicel, epoxy resin with butadiene structure), "ZX1658", "ZX1658GS" (the above are liquid 1,4-epoxypropyl cyclohexane type epoxy resins made by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd.) etc. These can be used alone or in combination of two or more.

Solid epoxy resins are preferably, for example, dimethylol epoxy resins, naphthalene epoxy resins, naphthalene tetrafunctional epoxy resins, cresol novolac epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol epoxy resins, biphenyl epoxy resins. , naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin, naphthol type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin can be cited. Specific examples include "HP4032H" (manufactured by DIC, naphthalene-based epoxy resin), "HP-4700", "HP-4710" (the above are naphthalene-based tetrafunctional epoxy resins manufactured by DIC), "N-690" (manufactured by DIC, cresol novolac-based epoxy resin), "N-695" (manufactured by DIC, cresol novolac-based epoxy resin), "HP-7200" (manufactured by DIC, dicyclopentadiene-based epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (the above are dicyclopentadiene-based epoxy resins manufactured by DIC esters), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all made by DIC Corporation, naphthyl ether type epoxy resin), "EPPN-502H" (made by Nippon Kayaku Corporation, trisphenol type epoxy resin), "NC-7000L", "NC-7300" (all made by Nippon Kayaku Corporation, naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (made by Nippon Kayaku Corporation, naphthol-cresol novolac type epoxy resin), The above are made by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin), "XD-1000-2L", "XD-1000-L", "XD-1000-H", "XD-1000-H" (the above are made by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (made by Nippon Steel Sumitomo Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (made by Nippon Steel Sumitomo Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (the above are made by Mitsubishi Chemical Co., Ltd., biphenyl type epoxy resin), " YX-4000HK" (Mitsubishi Chemical, bimethylol type epoxy resin), "YX-8800" (Mitsubishi Chemical, anthracene type epoxy resin), "PG-100", "CG-500" (Osaka Gas Chemical, fluorene type epoxy resin), "YL-7760" (Mitsubishi Chemical, bisphenol AF type epoxy resin), "YL-7800" (Mitsubishi Chemical, fluorene type epoxy resin), "jER1010" (Mitsubishi Chemical, solid bisphenol A type epoxy resin), "jER1031S" (Mitsubishi Chemical, tetraphenylethane type epoxy resin), etc. These can be used alone or in combination of two or more.

[Active ester compounds]

Active ester compounds refer to compounds that contain at least one ester bond in the structure and are bonded to aliphatic chains, aliphatic rings or aromatic rings on both sides of the ester bond. Examples of active ester compounds include compounds with two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxylamine esters, and esters of heterocyclic hydroxyl compounds. They can be obtained by condensation reaction of at least one of carboxylic acid compounds, acyl chlorides, or thiocarboxylic acid compounds with at least one of hydroxyl compounds or thiol compounds. In particular, from the perspective of improving heat resistance, it is preferred to obtain the compound from a carboxylic acid compound or acyl chloride and a hydroxyl compound, and the hydroxyl compound is preferably a phenolic compound or a naphthol compound. Active ester compounds can be used alone or in combination of two or more.

The above-mentioned carboxylic acid compounds include, for example, benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyrophyllic acid, etc.

Examples of the above-mentioned acyl chlorides include acetyl chloride, acryloyl chloride, methacryloyl chloride, malonyl chloride, succinyl chloride, 2,2'-oxydiacetyl chloride, glutaryl chloride, octanyl chloride, decanyl chloride, hexamethylene chloride, dodecane dichloride, nonanoyl chloride, 2,5-furan dicarbonyl chloride, o-phthalyl chloride, isophthalyl chloride, terephthalyl chloride, trimesic chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenylcarbonyl chloride, 4,4'-azodiphenylcarbonyl chloride, etc.

Examples of the phenol compound and the naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, acid phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, o-cresol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and the phenol resins described below. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

Preferred specific examples of active ester compounds include active ester compounds containing dicyclopentadiene diphenol structures, active ester compounds containing naphthalene structures, active ester compounds containing acetylated phenol novolacs, active ester compounds containing benzoylated phenol novolacs, compounds described in Example 2 of International Publication No. 2020/095829, and compounds disclosed in International Publication No. 2020/059625. Among them, active ester compounds containing naphthalene structures and active ester compounds containing dicyclopentadiene diphenol structures are more preferred. The dicyclopentadiene diphenol structure represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Examples of commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation) for active ester compounds containing a dicyclopentadiene-type diphenol structure, and "EXB9416-70BK" (manufactured by DIC Corporation) for active ester compounds containing a naphthalene structure. Examples of active ester compounds containing acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoylated phenol novolacs include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), active ester curing agents belonging to acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation), and active ester curing agents containing phosphorus atoms include "EXB-9050L-62M" manufactured by DIC Corporation, etc.

Regarding the blending ratio of active ester compounds and epoxy resins, the ratio (α/β) of active ester equivalent (α) to epoxy equivalent (β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. When the above range is exceeded, there is a risk of excess epoxy groups or active ester groups remaining in the system, and there is a risk of property deterioration in high temperature placement tests (150°C, 1000 hours, etc.) or long-term reliability tests under high temperature and high humidity conditions (temperature: 85°C, humidity: 85%, etc.).

[Phenolic resin]

Phenolic resin refers to a compound having two or more phenolic hydroxyl groups in the molecule. Examples of phenolic resins include, but are not limited to, reactants of phenols and aldehydes, reactants of phenols and diene compounds, reactants of phenols and ketones, reactants of phenols and substituted biphenyls, reactants of phenols and substituted benzenes, reactants of bisphenols and aldehydes, etc. Moreover, these may be used alone or in combination of multiple types.

The following are specific examples of the above raw materials, but are not limited to them.

<Phenols>

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

<Aldehydes>

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

<Diene compounds>

Dicyclopentadiene, terpenes, vinylcyclohexene, norbornene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropylbiphenyl, butadiene, isoprene, etc.

<Ketones>

Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, diphenyl ketone, fluorenone, etc.

<Substituted biphenyls>

4,4’-Bis(chloromethyl)-1,1’-biphenyl, 4,4’-Bis(methoxymethyl)-1,1’-biphenyl, 4,4’-Bis(hydroxymethyl)-1,1’-biphenyl, etc.

<Substituted benzene>

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

[Polyphenylene ether compounds]

From the perspective of heat resistance and electrical properties, the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylene unsaturated bond, and more preferably a polyphenylene ether compound having an acryl group, a methacryl group, or a styrene structure. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having a methacryl group) or OPE-2St1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styrene structure).

The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. When the molecular weight is less than 500, the cured product tends to have insufficient heat resistance. When the molecular weight is greater than 5000, the melt viscosity increases, and sufficient fluidity cannot be obtained, so it tends to be easy to form poorly. In addition, the reactivity will also decrease, the curing reaction takes a long time, and the unreacted products that do not enter the curing system increase, which reduces the glass transition temperature of the cured product and tends to reduce the heat resistance of the cured product.

When the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it can exhibit excellent heat resistance and moldability while maintaining excellent dielectric properties. In addition, the number average molecular weight can be specifically measured using gel permeation chromatography, etc.

The polyphenylene ether compound is obtained by polymerization reaction, and can be obtained by subjecting a high molecular weight polyphenylene ether compound having a number average molecular weight of about 10,000 to 30,000 to a redistribution reaction. In addition, the compound can be used as a raw material and reacted with a compound having an ethylenic unsaturated bond such as methacrylic chloride, acrylyl chloride, chloromethylstyrene, etc., thereby imparting free radical polymerizability. The polyphenylene ether compound obtained by the redistribution reaction can be obtained, for example, by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenol compound and a free radical initiator and subjecting it to a redistribution reaction. As mentioned above, the polyphenylene ether compound obtained by the redistribution reaction has hydroxyl groups from phenolic compounds at both ends of the molecular chain that participate in curing, so it can further maintain high heat resistance, and after modification with a compound having ethylenic unsaturated bonds, functional groups can also be introduced at both ends of the molecular chain, which is better. In addition, the polyphenylene ether compound obtained by the polymerization reaction shows excellent fluidity, which is better.

The molecular weight of the polyphenylene ether compound can be adjusted by adjusting the polymerization conditions when the polyphenylene ether compound is obtained by polymerization reaction. Furthermore, when the polyphenylene ether compound is obtained by redistribution reaction, the molecular weight of the obtained polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction. More specifically, it can be considered to adjust the amount of the phenolic compound used in the redistribution reaction. That is, the more the amount of the phenolic compound is blended, the lower the molecular weight of the obtained polyphenylene ether compound. At this time, the high molecular weight polyphenylene ether compound subjected to the redistribution reaction can use poly(2,6-dimethyl-1,4-phenylene ether) and the like. Furthermore, the phenolic compound used in the aforementioned redistribution reaction is not particularly limited. For example, it is preferred to use a multifunctional phenolic compound having two or more phenolic hydroxyl groups in the molecule such as bisphenol A, phenol novolac, cresol novolac, etc. These can be used alone or in combination of two or more.

[Amine resin]

Amine resin refers to a compound having two or more amino groups in the molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac (a reaction product of aniline and formalin), N-methylaniline novolac (a reaction product of N-methylaniline and formalin), o-ethylaniline novolac (a reaction product of o-ethylaniline and formalin), a reaction product of 2-methylaniline and formalin, a reaction product of 2,6-diisopropylaniline and formalin, a reaction product of 2,6-diethylaniline and formalin, a reaction product of 2-ethyl-6-ethylaniline and formalin, a reaction product of 2,6-dimethylaniline and formalin, a reaction product obtained by the reaction of aniline and xylene chloride. Aniline resin, reaction products of aniline and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.) described in Japanese Patent No. 6429862, reaction products of aniline and substituted benzenes (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-phenylene diisopropylidene)bisaniline, reaction products of aniline and diisopropylbenzene, dimer diamine, etc., but not limited to these. Moreover, these may be used alone or in combination of plural kinds.

[Compounds containing ethylenically unsaturated bonds]

Compounds containing ethylenically unsaturated bonds refer to compounds with one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light with or without a polymerization initiator.

Examples of compounds containing ethylenic unsaturated bonds include the reaction products of the aforementioned phenolic resin and halogen compounds containing ethylenic unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylyl chloride, methacrylic chloride, etc.), the reaction products of phenols containing ethylenic unsaturated bonds (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) and halogen compounds. Reaction products of compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorophenyl ketone, 4,4'-dichlorophenyl ketone, 4,4'-dibromophenyl ketone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols and (meth) acrylic acid (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof, but not limited to these. Moreover, these may be used alone or in combination of multiple types.

[Isocyanate resin]

Isocyanate resins refer to compounds with two or more isocyanate groups in the molecule. Examples of isocyanate resins include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,2-diisocyanate. Ester, diisocyanate, norbornene diisocyanate, lysine diisocyanate and other diisocyanates with aliphatic or alicyclic structures; biuret forms of one or more isocyanate monomers, or polyisocyanates such as isocyanate forms obtained by trimerization of the above diisocyanate compounds, and polyisocyanates obtained by urethanization of the above isocyanate compounds with polyol compounds, but not limited to these. Moreover, these can be used alone or in combination of multiple types.

[Polyamide resin]

唑啉之任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。又，該等可使用1種或併用複數種。 Examples of polyamide resins include diamines, diisocyanates,

The reaction products of any one or more of oxazoline and dicarboxylic acid, the reaction products of diamine and acyl chloride, and the ring-opening polymer of lactam compound. These may be used alone or in combination of plural kinds.

The following are specific examples of the above raw materials, but are not limited to them.

<Diamine>

Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane, dimer diamine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylene diamine, norbornane diamine, isophorone diamine, bisaminomethyl tricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalene diamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane bis(4-amino-3,5-diethylphenyl)methane, 4,4'-methylenebis-o-toluidine, 4, 4'-Methylenebis-o-ethylaniline, 4,4'-Methylenebis-2-ethyl-6-methylaniline, 4,4'-Methylenebis-2,6-diisopropylaniline, 4,4-ethylenediphenylamine, diaminodiphenylsulfone, 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-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminodiphenyl ketone, etc.

<Diisocyanate>

Benzene 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, dicyclohexylmethane-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, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfonate of isophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalene dicarboxylic acid, diphenyl ketone dicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxy diphenyl ether, 4,4'-dicarboxy diphenyl sulfide, etc.

<Acyl chloride>

Acetyl chloride, acryloyl chloride, methacryloyl chloride, malonic acid chloride, dichloro succinyl chloride, 2,2'-oxydiacetyl chloride, glutaric acid chloride, octanedichlor, decanedichlor, hexamethylenedichlor, dodecanedichlor, nonanoyl chloride, 2,5-furandicarbonyl chloride, o-phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenylcarbonyl chloride, 4,4'-azodiphenylcarbonyl chloride, etc.

<Lactamide>

ε-caprolactam, ω-undecane lactam, ω-lauryl lactam, etc.

[Polyimide resin]

Examples of polyimide resins include, but are not limited to, the reaction products of the aforementioned diamine and the tetracarboxylic dianhydride exemplified below. Moreover, these may be used alone or in combination of multiple types.

<Tetracarboxylic dianhydride>

4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromelitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketonetetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonatetetracarboxylic dianhydride , 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'-diphthalic dianhydride, 2,2'-propylene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene -4,4'-diphthalic acid anhydride, 4,4'-oxydiphthalic acid anhydride, thio-4,4'-diphthalic acid anhydride, sulfonyl-4,4'-diphthalic acid anhydride, 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)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-dicarboxyphenoxy) 4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, Cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4' -bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, rel-[1 S,5R,6R]-3-oxobicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, ethylene glycol-bis-(3,4-dicarboxylic anhydride phenyl) ether, 4,4'-biphenyl bis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[Maleimide compounds]

The curable resin composition of the present invention may contain a maleimide compound. The maleimide compound is a compound having one or more maleimide groups in the molecule. Examples of the maleimide compound include 4,4'-diphenylmethane dimaleimide, polyphenylmethane maleimide, metaphenylene dimaleimide, 2,2'-bis[4-(4-maleimidephenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane dimaleimide, 4-methyl -1,3-phenylene bismaleimide, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene), Zylock type maleimide compounds (ANILIX-MI, MITSUI FINE CHEMICALS Co., Ltd.), biphenyl aralkyl type maleimide compound (solidified by distilling off the solvent from the resin solution containing the maleimide compound (M2) described in Example 4 of Japanese Patent Publication No. 2009-001783 under reduced pressure), diamino isopropylphenyl type maleimide (maleimide compound described in International Publication No. 2020/054601), maleimide compound with indane structure described in Japanese Patent No. 6629692 or International Publication No. 2020/217679, MATERIAL STAGE Vol.18, No.12 2019 『To be continued． Maleimide compounds described in "Epoxy resin CAS number description to hardener CAS number memorandum, No. 31, dimaleimide (1)" or MATERIAL STAGE Vol.19, No.2 2019 "Continued. Epoxy resin CAS number description to hardener CAS number memorandum, No. 32, dimaleimide (2)", etc., but are not limited to them. Moreover, these can be used alone or in combination of plural types.

[Cyanate resin]

The cyanate resin is a cyanate compound obtained by reacting a phenol resin with a cyanide halogen. Specific examples thereof include dicyanate benzene, tricyanate benzene, dicyanate naphthalene, dicyanate biphenyl, 2,2'-bis(4-cyanate phenyl)propane, bis(4-cyanate phenyl)methane, bis(3,5-dimethyl-4-cyanate phenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanate phenyl)propane, 2,2'-bis(4-cyanate phenyl)ethane, 2,2'-bis(4-cyanate phenyl)hexafluoropropane, bis(4-cyanate phenyl)sulfide, bis(4-cyanate phenyl)sulfide, phenol novolac cyanate, and a product obtained by converting the hydroxyl group of a phenol/dicyclopentadiene copolymer into a cyanate group. However, the present invention is not limited to the foregoing. Furthermore, one or more of these may be used.

In addition, the cyanate compound described in the synthesis method in Japanese Patent Publication No. 2005-264154 has low hygroscopicity, flame retardancy, and excellent dielectric properties, so it is particularly suitable as a cyanate compound.

環而含有環烷酸鋅、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。 Cyanate resins can optionally be used to trimerize the cyanate groups to form sym-trimers.

The ring contains catalysts such as zinc cycloalkanoate, cobalt cycloalkanoate, copper cycloalkanoate, lead cycloalkanoate, zinc octanoate, tin octanoate, lead acetylacetonate, and dibutyltin maleate.

The catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, based on 100 parts by mass of the cyanate resin and the curable resin composition.

[Polybutadiene and its modified products]

Polybutadiene and its modified products refer to compounds with polybutadiene or polybutadiene-derived structures in the molecule. The structures derived from polybutadiene can convert part or all of the unsaturated bonds into single bonds by hydrogenation.

Polybutadiene and its modified products include polybutadiene, hydroxyl-terminated polybutadiene, terminal (meth) acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene butadiene rubber, etc., but are not limited to them. In addition, these can be used in one or in combination. Among them, from the perspective of dielectric properties, polybutadiene or styrene butadiene rubber is preferred. Styrene butadiene rubber (SBR) includes RICON-100, RICON-181, RICON-184 (all made by CRAY VALLEY), 1,2-SBS (made by Nippon Soda Co., Ltd.), etc., and polybutadiene includes B-1000, B-2000, B-3000 (all made by Nippon Soda Co., Ltd.), etc. The molecular weight of polybutadiene and styrene butadiene rubber is preferably 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000 in terms of weight average molecular weight. Below the lower limit of the above range, the volatility is large, and it is difficult to adjust the solid content when making a prepreg. Above the upper limit of the above range, the compatibility with other curing resins will deteriorate. Generally speaking, when it is a compound containing impurities such as oxygen or nitrogen, such as dimaleimide or polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds composed only of hydrocarbons due to their polarity. On the other hand, the compound of the present invention itself does not actively introduce oxygen or nitrogen into the skeleton design, so it has excellent compatibility with low-polarity and low-dielectric materials or compounds composed only of hydrocarbons.

[Polystyrene and its modified products]

Polystyrene and its modified products refer to compounds that have the structure of polystyrene or are derived from polystyrene in the molecule.

唑啉共聚物(Epocros RPS-1005、RP-61，皆為日本觸媒公司製)、SEP(苯乙烯/乙烯/丙烯共聚物：Septon 1020，Kuraray公司製)、SEPS(苯乙烯/乙烯/丙烯/苯乙烯共聚物：Septon 2002、Septon 2004F、Septon 2005、Septon 2006、Septon 2063、Septon 2104，皆為Kuraray公司製)、SEEPS(苯乙烯/乙烯/乙烯/丙烯/苯乙烯嵌段共聚物：Septon 4003、Septon 4044、Septon 4055、Septon 4077、Septon 4099，皆為Kuraray公司製)、SEBS(苯乙烯/乙烯/丁烯/苯乙烯嵌段共聚物：Septon 8004、Septon 8006、Septon 8007L，皆為Kuraray公司製)、SEEPS-OH(於苯乙烯/乙烯/乙烯/丙烯/苯乙烯嵌段共聚物之末端具有羥基之化合物：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，皆為Kuraray公司製)、氫化SIS(氫化苯乙烯/異戊二烯/苯乙烯嵌段共聚物：Hybrar 7125F、Hybrar 7311F，皆為Kuraray公司製)、SIBS(苯乙烯/異丁烯/苯乙烯嵌段共聚物：SIBSTAR073T、SIBSTAR102T、SIBSTAR103T(皆為kaneka公司製)、Septon V9827(Kuraray公司製))等，但並不限定於該等。又，該等可使用1種或併用複數種。具有較高耐熱性且不易氧化，故聚苯乙烯及其改質物較佳為不具有不飽和鍵者。又，聚苯乙烯及其改質物之重量平均分子量為10000以上則無特別限制，但若過大則除了與聚苯醚化合物的相容性惡化以外，與重量平均分子量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也會惡化，難以確保混合及溶劑穩定性，因此較佳為10000至300000左右。 Polystyrene and its modified products include polystyrene, styrene, 2-isopropenyl-2-

Oxazoline copolymers (Epocros RPS-1005, RP-61, both manufactured by Nippon Catalyst Co., Ltd.), SEP (styrene/ethylene/propylene copolymer: Septon 1020, manufactured by Kuraray), SEPS (styrene/ethylene/propylene/styrene copolymers: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray), SEEPS (styrene/ethylene/ethylene/propylene/styrene block copolymers: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099, all manufactured by Kuraray), SEBS (styrene/ethylene/butylene/styrene block copolymers: Septon 8004, Septon 8006, Septon 8007L, both manufactured by Kuraray Co., Ltd.), SEEPS-OH (a compound having a hydroxyl group at the end of a styrene/ethylene/ethylene/propylene/styrene block copolymer: Septon HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene/isoprene/styrene block copolymers: Septon 5125, Septon 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene/isoprene/styrene block copolymers: Hybrar 7125F, Hybrar 7311F, both manufactured by Kuraray Co., Ltd.), SIBS (styrene/isobutylene/styrene block copolymers: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Co., Ltd.), Septon V9827 (manufactured by Kuraray Co., Ltd.)), etc., but are not limited to them. Moreover, these can be used alone or in combination. Polystyrene and its modified products preferably have no unsaturated bonds because they have high heat resistance and are not easily oxidized. Moreover, the weight average molecular weight of polystyrene and its modified products is not particularly limited to 10,000 or more, but if it is too large, in addition to deterioration of compatibility with polyphenylene ether compounds, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will also deteriorate, making it difficult to ensure mixing and solvent stability, so it is preferably about 10,000 to 300,000.

[Polyethylene and its modified products]

Polyethylene and its modified products refer to compounds having a structure of polyethylene or derived from polyethylene in the molecule. Examples of polyethylene and its modified products include ethylene/propylene copolymers, ethylene/styrene copolymers, ethylene/propylene/ethylidene norbornene copolymers (manufactured by Mitsui Chemicals, EBT: K-8370EM, K-9330M, etc.), ethylene/propylene/vinyl norbornene copolymers (manufactured by Mitsui Chemicals, VNB-EPT: PX-006M, PX-008M, PX-009M, etc.), ethylene/vinyl alcohol copolymers, ethylene/vinyl acetate copolymers, etc., but are not limited thereto. From the viewpoint of improving heat resistance, it is preferred to use ethylene/propylene/ethylidene norbornene copolymers and ethylene/propylene/vinyl norbornene copolymers having a crosslinkable structure. Moreover, these can be used alone or in combination of a plurality of types. There is no special restriction on the weight average molecular weight of polyethylene and its modified products when it is above 10,000. If it is too large, in addition to the deterioration of compatibility with polyphenylene ether compounds, the compatibility with low molecular weight components with a weight average molecular weight of about 50 to 1,000 and oligomer components with a weight average molecular weight of about 1,000 to 5,000 will also deteriorate, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.

The curable resin composition of the present invention can be obtained by mixing the above-mentioned components in a specific ratio, pre-curing at 130 to 180°C and 30 to 500 seconds, and further post-curing at 150 to 200°C for 2 to 15 hours, and the cured product of the present invention can be obtained by post-curing to fully perform the curing reaction. In addition, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, etc., and cured after removing the solvent.

The preparation method of the curable resin composition of the present invention is not particularly limited. The components may be simply mixed uniformly or prepolymerized. For example, the mixture containing the compound of the present invention is heated in the presence or absence of a curing accelerator or a polymerization initiator, in the presence or absence of a solvent, thereby prepolymerizing. Similarly, amine compounds, compounds having ethylenic unsaturated bonds, maleimide compounds, cyanate compounds, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives may be added and prepolymerized. The mixing or prepolymerization of the components is carried out in the absence of a solvent using, for example, an extruder, a kneader, a roller, etc., and in the presence of a solvent using a reaction kettle with a stirring device, etc.

The uniform mixing method can be used to mix and form a uniform resin composition by kneading at a temperature within the range of 50 to 100°C using a kneader, roller, planetary mixer, etc. The obtained resin composition is crushed and then formed into a cylindrical tablet in a molding machine such as a tablet press, or formed into a granular powder or powder molding, or the composition is melted on a surface support and molded into a thin sheet with a thickness of 0.05mm to 10mm to form a hardening resin composition molding. The obtained molding is a non-sticky molding at 0 to 20°C, and even if it is stored at -25 to 0°C for more than 1 week, the fluidity and hardening properties are almost not reduced.

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

The curable resin composition of the present invention may also be added with an organic solvent to form a varnish-like composition (hereinafter referred to as varnish). The curable resin composition of the present invention may be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. as needed to form a varnish, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heated and dried to obtain a prepreg, and then the prepreg is hot-pressed to form a cured product of the curable resin composition of the present invention. The solvent at this time is preferably used in a mixture of the curable resin composition of the present invention and the solvent in an amount of 10 to 70% by weight, preferably 15 to 70% by weight. In addition, if it is a liquid composition, a cured curable resin containing carbon fibers can be directly obtained, for example, by RTM.

Furthermore, the curable resin composition of the present invention can also be used as a modifier for film-type compositions. Specifically, it can be used to improve the flexibility in the B stage. The film-type resin composition can be obtained by applying the curable resin composition of the present invention as a varnish on a release film, removing the solvent under heating, and then performing the B stage, thereby obtaining a thin sheet adhesive. The thin sheet adhesive can be used as an interlayer insulating layer in a multi-layer substrate, etc.

唑、聚醯亞胺及碳纖維等有機纖維，但不限定於該等。基材之形狀並無特別限定，可舉例如織布、不織布、粗紗、切股氈等。又，織布之織法已知有平織、斜子紋織、斜紋織等，可由該等習知者因應目的用途及性能而適當地選擇使用。又，亦適合使用將織布解纖處理者或以矽烷耦合劑等表面處理的玻璃織布。基材之厚度並無特別限定，較佳為0.01至0.4mm左右。又，可將前述清漆含浸於強化纖維並加熱乾燥，藉此獲得預浸體。 The curable resin composition of the present invention can also be melted by heating and reduced in viscosity, and then impregnated into reinforcing fibers such as glass fibers, carbon fibers, polyester fibers, polyamide fibers, and alumina fibers to obtain a prepreg. Specific examples thereof include glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, and inorganic fibers other than glass, or polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoate, and polyparaphenylene terephthalamide.

Organic fibers such as azoles, polyimide and carbon fibers, but not limited to them. The shape of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, coarse yarns, chopped strands of felt, etc. Furthermore, the weaving methods of woven fabrics are known to include plain weave, twill weave, and twill weave, etc., and those skilled in the art can appropriately select and use them according to the intended use and performance. Furthermore, it is also suitable to use glass fabrics that have been subjected to a defiberizing treatment on the fabric or a surface treatment with a silane coupling agent, etc. The thickness of the substrate is not particularly limited, and is preferably about 0.01 to 0.4 mm. Furthermore, the aforementioned varnish can be impregnated into the reinforcing fibers and heated and dried to obtain a prepreg.

Furthermore, the above-mentioned prepreg can also be used to manufacture a laminate. The laminate is not particularly limited as long as it has one or more prepregs, and can have any other layers. The manufacturing method of the laminate can appropriately apply the generally known method, and is not particularly limited. For example, when forming the metal foil laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, a high-pressure autoclave molding machine, etc. can be used to stack the above-mentioned prepregs on each other and heat and pressurize them to obtain a laminate. The heating temperature at this time is not particularly limited, and is preferably 65 to 300°C, and more preferably 120 to 270°C. Furthermore, there is no particular limit to the pressurization pressure. If the pressure is too high, it will be difficult to adjust the solid content of the resin of the laminate, and the quality will be unstable. If the pressure is too low, bubbles will be generated or the adhesion between the layers will deteriorate. Therefore, it is preferably 2.0 to 5.0 MPa, and more preferably 2.5 to 4.0 MPa. The laminate of this embodiment has a layer composed of metal foil, so it is suitable for use as a metal foil-clad laminate described later.

After the above-mentioned prepreg is cut into the desired shape and laminated with copper foil etc. as needed, pressure is applied to the laminate by press molding, high pressure autoclave molding, sheet winding molding, etc., while the curable resin composition is heated and cured, thereby obtaining a laminate (printed circuit board) or carbon fiber reinforced material for electrical and electronic use.

The hardening resin composition of the present invention can also be formed into a resin sheet. The method of obtaining the resin sheet from the hardening resin composition of the present invention includes, for example, coating the hardening resin composition on a supporting film (support body) and then drying it to form a resin composition layer on the supporting film. When the curable resin composition of the present invention is used for a resin sheet, it is important that the film softens under the lamination temperature conditions (70°C to 140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that allows resin filling in via holes or through holes in the display circuit substrate while laminating with the circuit substrate. It is preferred to blend the aforementioned components in a manner that exhibits this characteristic. In addition, in the obtained resin sheet or circuit substrate (copper-clad laminate, etc.), in order to avoid the phenomenon of locally showing different characteristic values due to phase separation, etc., and to exhibit fixed performance in any part, appearance uniformity is required.

Here, the diameter of the through hole of the circuit substrate is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm. It is better to fill the resin within this range. In addition, when laminating the two sides of the circuit substrate, it is better to fill about 1/2 of the through hole.

A specific method for manufacturing the aforementioned resin sheet includes mixing an organic solvent and preparing a varnished resin composition, applying the varnished resin composition on the surface of a support film (Y), and further drying the organic solvent by heating or blowing hot air to form a resin composition layer (X).

The organic solvent used here is preferably ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc., carbitols such as cellosol and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. In addition, it is preferred to use the organic solvent at a ratio of 30 to 60 mass % of the total non-volatile matter.

Furthermore, the thickness of the aforementioned resin composition layer (X) formed needs to be greater than the thickness of the conductor layer of the circuit substrate on which the aforementioned resin composition layer (X) is laminated. The thickness of the conductor layer of the circuit substrate is in the range of 5 to 70 μm, so the thickness of the aforementioned resin composition layer (X) is preferably 10 to 100 μm. Furthermore, the aforementioned resin composition layer (X) in the present invention can be protected by a protective film described later. By protecting with a protective film, it is possible to prevent waste or scratches on the surface of the resin composition layer (X).

The supporting film and protective film mentioned above can include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonate, polyimide, and mold release paper or metal foils such as copper foil and aluminum foil. In addition, the supporting film and protective film can be subjected to matte treatment, corona treatment, and mold release treatment. The thickness of the supporting film is not particularly limited, but can be 10 to 150 μm, 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 supporting film (Y) can be peeled off after laminating the resin composition layer (X) on the circuit substrate or after the resin composition layer (X) is heat-cured to form an insulating layer. If the supporting film (Y) is peeled off after the resin composition layer (X) constituting the resin sheet is heat-cured, the attachment of waste materials in the curing step can be prevented. When the supporting film (Y) is peeled off after the resin composition layer (X) is heat-cured, the supporting film (Y) can be subjected to a demolding treatment in advance.

1至11kgf/cm²(9.8×10⁴至107.9×10⁴N/m²)，較佳為在空氣壓為20mmHg(26.7hPa)以下之減壓下層合。 Furthermore, a multi-layer printed circuit substrate can be manufactured from the resin sheet obtained in the aforementioned manner. For example, when the aforementioned resin composition layer (X) is protected by a protective film, after the protective film is peeled off from the resin composition layer (X), the aforementioned resin composition layer (X) can be directly in contact with the circuit substrate and laminated on one or both sides of the circuit substrate, for example, by a vacuum lamination method. The lamination method can be a batch method or a continuous method using a roller. Furthermore, the resin sheet and the circuit substrate can be heated (preheated) as needed before lamination. The lamination conditions are preferably a pressing temperature (lamination temperature) of 70 to 140°C and a pressing pressure of

1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ), preferably laminated under reduced pressure of 20 mmHg (26.7 hPa) or less.

Furthermore, the curable resin composition of the present invention can be used to manufacture semiconductor devices. Examples of semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), TQFP (thin quad flat package), etc.

The curable resin composition and its cured product of the present invention can be used in a wide range of fields. Specifically, it can be used for various purposes such as molding materials, adhesives, composite materials, coatings, etc. The cured product of the curable resin composition described in the present invention shows excellent heat resistance and dielectric properties, so it is suitable for use in electrical and electronic parts such as sealing materials for semiconductor components, sealing materials for liquid crystal display components, sealing materials for organic EL components, laminates (printed circuit boards, BGA substrates, build-up substrates, etc.) or composite materials for lightweight and high-strength structural materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.

(Implementation example)

Next, the present invention is further described in detail by way of examples. Hereinafter, parts are parts by mass unless otherwise specified. Furthermore, the present invention is not limited to the examples.

The various analytical methods used in the examples are described below.

‧GPC (Gel Permeation Chromatography) Analysis

Equipment: Online degassing unit (DGU-20A), liquid delivery unit (LC-20AD), automatic sample injector (SIL-20A), photodiode array detector (SPD-M40), column oven (CTO-20A), system controller (CBM-20A), all manufactured by Shimadzu Corporation

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

Flow rate: 1.5ml/min.

Column temperature: 40℃

Solvent used: THF (tetrahydrofuran)

Detector: Differential refractometer (RID-20A), manufactured by Shimadzu Corporation

[Implementation Example 1]

A vacuum pump and an alkali collector were installed in a flask equipped with a thermometer, a cooling tube, and a stirrer. 20 parts of Tuftec M1913 (manufactured by Asahi Kasei Co., Ltd.), 180 parts of toluene, and 0.34 parts of allylamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) of acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) were added to the flask, and the generated hydrogen chloride was captured with an alkali collector while reacting at 110°C for 12 hours. After cooling, the obtained reaction solution was dripped into 1L of acetone to reprecipitate. After drying at room temperature for 12 hours, 18.2g of the target compound (AA) (light yellow solid) was obtained. (Mn: 69462, Mw: 95623). The GPC diagram of the obtained compound is shown in Figure 1.

[Implementation Examples 2, 3, Comparative Examples 1, 2]

The compound (AA) obtained in Example 1, polyphenylene ether compound: SA-9000 (manufactured by SABIC), styrene butadiene rubber: Ricon-100 (manufactured by CRAY VALLEY), and polymerization initiator: diisopropylbenzene peroxide (DCP) were used in the amounts shown in Table 1. In Examples 2 and 3, a toluene solution with a solid content of 30% by weight was prepared. In Comparative Examples 1 and 2, a toluene solution with a solid content of 70% by weight was prepared. The toluene solution was applied to a mirror copper foil (T4X: manufactured by Futian Metal Copper Foil Co., Ltd.) using a coating applicator with a coating thickness of 200 μm, and then cured at 220°C in an inert oven for 2 hours to obtain a cured product. When evaluating, a test piece of the required size was cut out using a laser cutter as needed and implemented.

<Loss tangent test>

A 10 GHz cavity resonator manufactured by AET Co., Ltd. was used to conduct the test at 25°C using the cavity resonator perturbation method. The sample size was 1.7 mm wide x 100 mm long, and the test was conducted with a thickness of 0.3 mm. The evaluation results are shown in Table 1.

[Table 1]

‧SA-9000: Terminal methacrylic acylated polyphenylene ether (manufactured by SABIC)

‧Ricon-100: Styrene butadiene rubber (manufactured by CRAY VALLEY)

‧DCP: diisopropylbenzene peroxide

The results in Table 1 show that compared with Comparative Examples 1 and 2, the compound (AA) obtained in Example 1 has a smaller loss tangent and excellent low dielectric properties.

This case claims priority based on Japanese Patent Application No. 2023-15088 filed on February 3, 2023.

(Industrial availability)

The compound of the present invention is suitable for use in semiconductor sealing materials, printed wiring boards, build-up laminates and other electrical and electronic components.

Claims (11)

A compound obtained by reacting an acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) with allylamine or allylamine hydrochloride, wherein the acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) is an acid-modified product of a hydrogenated product (H-AB) of a block copolymer, and the block copolymer is composed of a block unit (A) of a polymer containing a styrene monomer and a block unit (B) of a polymer containing a conjugated diene compound. The compound as described in claim 1, wherein the block unit (A) of the polymer containing styrene monomers is a structure represented by the following formula (a),

In formula (1), _R1 and _R2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, p is 1 to 5, and q is an average value of repeated numbers and represents a real number from 1 to 10,000. The compound as described in claim 1, wherein the block unit (B) of the polymer containing the conjugated diene compound is obtained by polymerizing at least one diene compound selected from 1,3-butadiene, isoprene, acaciaene, 2,3-dimethyl-1,3-butadiene, and 1,3-pentadiene. The compound as described in claim 1, wherein the hydrogenated product (H-AB) of the aforementioned block copolymer is a compound represented by the following formula (1),

In formula (1), _R1 and _R2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, respectively, p is 1 to 5, j, k, l, m, and n are average values of repetition numbers and represent real numbers from 1 to 10,000, and the order of the repetition units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern may be any of alternating, block, and random. The compound as described in claim 1, wherein the aforementioned acid-modified hydrogenated thermoplastic styrene elastomer (AH-AB) is a compound represented by the following formula (2),

In formula (2), _R1 and _R2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, respectively, p is 1 to 5, j, k, l, m, and n are average values of repetition numbers and represent real numbers from 1 to 10,000, and the order of the repetition units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random. A compound is represented by the following formula (3),

In formula (3), _R1 and _R2 are hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, respectively, p is 1 to 5, j, k, l, m, and n are average values of repetition numbers and represent real numbers from 1 to 10,000, and the order of the repetition units in parentheses with k and l, or j, m, and n as subscripts is not limited, and the bonding pattern can be any of alternating, block, and random. A hardening resin composition containing a compound as described in any one of claims 1 to 6. The hardening resin composition as described in claim 7 further contains a polymerization initiator. The curable resin composition as described in claim 7 or 8 further contains at least one selected from maleimide compounds, polyphenylene ether compounds, compounds having ethylenic unsaturated bonds, cyanate resins, polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products. A hardened material, which is a hardened material of a compound as described in any one of claims 1 to 6. A hardened product, which is a hardened product of the hardening resin composition as described in any one of claims 7 to 9.

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