TW201803918A - Thermosetting resin, its composition and use wherein the thermosetting resin is obtained from a diamine compound reacted with a bismaleimide - Google Patents

Abstract

The present invention provides a thermosetting resin obtained from a diamine compound reacted with a bismaleimide, and a thermosetting resin composition comprising: (a) a compound having two unsaturated groups, (b) a flame retardant, and (c) a thermosetting resin. The present invention is provided to produce adhesives for laminates and copper, semiconductor packaging materials, flexible substrates, cover films, binding sheets, sealants, pure glue films, rigid-flex boards, solder resist ink, high-frequency flexible substrates, high-frequency substrates, adhesives for laminates and copper, pre-impregnated sheets, IC substrates, in-vehicle substrates, and so on.

Description

Thermosetting resin and its composition and use

The present invention provides a thermosetting resin and a composition thereof. The composition contains at least: (a) a compound containing two unsaturated groups, (b) a flame retardant, and (c) a thermosetting resin. Adhesives for boards, copper foils, semiconductor construction materials, flexible substrates, cover films, adhesive sheets, sealants, pure adhesive films, flexible and rigid boards, solder masks, high-frequency flexible substrates, high-frequency substrates, Laminates, adhesives for copper foil, prepregs, IC substrates, automotive boards, etc.

With the advancement of communication and electronic technology, the signal transmission of large computers, mobile communications, base stations, servers, routers, and intelligent vehicle intelligent transmission systems (ITS) has developed toward higher frequencies and higher speeds. Among them, low-dielectric resin materials It has become a key material in high-speed transmission technology. Its low dielectric constant (Dk) will affect the speed of signal transmission, and its low dielectric loss (Df) will affect the quality of signal transmission. The trend of mobile communication devices is high speed, thin and light, high Density substrates replace traditional substrates. The substrates are becoming extremely thin, multilayered, high-density, and the semiconductors are embedded. The substrate materials and packaging materials require higher glass transition temperatures and lower dielectric properties. Properties such as flexibility, elastic modulus, etc., among which the elastic modulus and the expansion coefficient will affect the warpage of the semiconductor package substrate, and the elastic modulus will also directly affect the substrate toughness and the reliability of the holes.

Patent document CN102993491-A discloses a thermosetting resin composition that improves the metal bonding strength of phenol-based polyphenylene ether with a butadiene polymer, and has a Df of 0.003 or more and a Dk of 3.2 or more.

Patent document TW201546181 discloses a resin composition containing (A) a polyimide resin, (B) a prepolymerized maleimide resin, (C) a thermosetting resin, (D) a flame retardant, and a Df of 0.007 or more, Dk is above 2.9.

Among the known resin materials, only vinyl polyphenylene ether (TWI250995) has better dielectric properties (Dk about 2.6, Df about 0.003), and the glass transition temperature can reach about 180 ° C. It is technically difficult to improve the glass transition temperature and elasticity at the same time with low dielectric properties, or the toughness, folding resistance of vinyl polyphenylene ether, and the adhesion to polyimide film and copper foil There is still much room for improvement.

One of the problems to be solved by the present invention is that one of the problems existing in the prior art is that although polyphenylene ether and polytetrafluoroethylene can meet the industrial requirements of low dielectric loss Df (1GHz) below 0.004, the polyphenylene ether itself is too brittle , The folding resistance and bonding strength are not good, and PTFE is not easy to process. The two are not sufficient for flexible substrates and cannot meet the expectations and demands of the industry. The second is the problems of the previous technology, which are widely used. Although the cured polyphenylene ether resin and composition on a high-frequency substrate have low dielectric loss (Df) and low dielectric constant (Dk), its glass transition temperature is below 180 ° C and the substrate is extremely thin. In order to solve the problem of difficult heat dissipation, it is necessary to increase the glass transition temperature. In order to respond to the extreme thinning, the tear strength and flexural elasticity must be increased to meet the technical trend. Requirements for next-generation high-frequency substrates and semiconductor packaging materials.

其中R1、R2、R3、R4為相同或不相同，且表示為氫、甲基、乙基、丙基；雙馬來醯亞胺為：

；二胺化合物為：H₂N-A-NH₂；A選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；X為選自：

、

、C24~C48具脂肪族側鏈之二價烴基，所組成組群之一或多種；B為選自：

所組成組群之一或多種；Y為選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；Z為選自：

、

、C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；n為選自：1~1000的整數；m為選自：1~1000的整數；p為選自：0~1000的整數；q為選自：1~1000的整。 The technical means for solving the problem of the present invention is to provide a thermosetting resin, which is obtained by reacting a diamine compound with bismaleimide, and is characterized in that the molecule contains at least one chemical structural residue as shown in formula (1). base:

R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, methyl, ethyl, and propyl; bismaleimide is:

; The diamine compound is: H ₂ NA-NH ₂ ; A is selected from:

C16 ~ C44 have a divalent hydrocarbon group with an aliphatic side chain, which constitutes one or more groups; X is selected from:

,

, C24 ~ C48 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; B is selected from:

One or more of the groups formed; Y is selected from:

C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; Z is selected from:

,

, C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; p is selected from: An integer from 0 to 1000; q is an integer selected from: 1 to 1000.

一分子中至少含有有二個N-取代馬來醯亞胺基之馬來醯亞胺化和物，所組成組群之一或多種；(b)難燃劑，其包括：

(c)熱固性樹脂，其係由二胺化合物與雙馬來醯亞胺反應所獲致，其特徵在於分子中至少含有一個如式(一)所示之化學結構殘基：

其中R1、R2、R3、R4為相同或不相同，且表示為氫、甲基、乙基、丙基；雙馬來醯亞胺為：

；二胺化合物為：H₂N-A-NH₂；A選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；X為選自：

、

、C24~C48具脂肪族側鏈之二價烴基，所組成組群之一或多種；B為選自：

所組成組群之一或多種；Y為選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；Z為選自：

、

、C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；n為選自：1~1000的整數；m為選自：1~1000的整數；p為選自：0~1000的整數；q為選自：1~1000的整。 The present invention provides a thermosetting resin composition. The composition includes at least: (a) a compound containing two unsaturated groups, including:

A molecule containing at least two N-substituted maleimide imino groups in one molecule, one or more of the group consisting of; (b) a flame retardant, including:

(c) A thermosetting resin, which is obtained by reacting a diamine compound with bismaleimide, and is characterized in that it contains at least one chemical structure residue represented by formula (1) in the molecule:

R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, methyl, ethyl, and propyl; bismaleimide is:

; The diamine compound is: H ₂ NA-NH ₂ ; A is selected from:

C16 ~ C44 have a divalent hydrocarbon group with an aliphatic side chain, which constitutes one or more groups; X is selected from:

,

, C24 ~ C48 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; B is selected from:

One or more of the groups formed; Y is selected from:

C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; Z is selected from:

,

, C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; p is selected from: An integer from 0 to 1000; q is an integer selected from: 1 to 1000.

The application of the present invention is to provide a thermosetting resin, which is used for manufacturing a build-up board, Adhesives for copper foil, semiconductor construction materials, flexible substrates, cover films, adhesive sheets, sealants, pure adhesive films, flexible and rigid boards, solder masks, high-frequency flexible substrates, etc.

The invention provides the use of a thermosetting resin composition, which is used for manufacturing laminated boards, high-frequency substrates, build-up boards, adhesives for copper foil, prepregs, semiconductor structural materials, IC substrates, and automotive applications. Board, etc.

Compared with the efficacy of the prior art, one is that although vinyl polyphenylene ether and polytetrafluoroethylene can meet the industrial requirements of low dielectric loss Df (1GHz) below 0.003, the polyphenylene ether itself is too brittle, folding resistance and adhesion strength Poor, polytetrafluoroethylene is not easy to process, and their characteristics are not sufficient for flexible substrates, which cannot meet the industry's expectations and needs. The present invention provides a thermosetting resin with low dielectric properties, high adhesion, Folding resistance and other characteristics, meet the requirements of the next generation of high-frequency flexible substrates; the other is the polyphenylene ether resin and the cured product of the composition, which are widely used in high-frequency substrates, and have low dielectric loss (Df) and low dielectric constant (Dk), but the glass transition temperature is below 180 ° C. The present invention provides a composition and a cured product thereof having flame retardancy, low dielectric loss (Df), low dielectric constant (Dk), and higher glass transition. , Tear strength and flexural elasticity, can meet the requirements of the next generation of high-frequency substrates and semiconductor packaging materials and the industry's eager expectations.

其中R1、R2、R3、R4為相同或不相同，且表示為氫、甲基、乙基、丙基；雙馬來醯亞胺為：

；二胺化合物為：H₂N-A-NH₂；A選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；X為選自：

、

、C24~C48具脂肪族側鏈之二價烴基，所組成組群之一或多種；B為選自：

所組成組群之一或多種；Y為選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；Z為選自：

、

、C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；n為選自：1~1000的整數；m為選自：1~1000的整數；p為選自：0~1000的整數；q為選自：1~1000的整。 The invention provides a thermosetting resin, which is obtained by a reaction between a diamine compound and bismaleimide, and is characterized in that the molecule contains at least one chemical structure residue represented by formula (1):

R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, methyl, ethyl, and propyl; bismaleimide is:

; The diamine compound is: H ₂ NA-NH ₂ ; A is selected from:

C16 ~ C44 have a divalent hydrocarbon group with an aliphatic side chain, which constitutes one or more groups; X is selected from:

,

, C24 ~ C48 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; B is selected from:

One or more of the groups formed; Y is selected from:

C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; Z is selected from:

,

, C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; p is selected from: An integer from 0 to 1000; q is an integer selected from: 1 to 1000.

The invention provides a thermosetting resin, which is composed of a diamine compound and bismaleimide at 50 ° C to 180 ° C for Michael addition reaction (reaction 1), and a linear structure is formed. At the same time, there may be a small amount of maladia Side reaction of the addition of amine double bond with secondary amine (Reaction 2). When cured at 180 ℃ ~ 230 ℃, the maleimide imide double bond will be opened, and free radicals of maleimide Polymerization reaction (Reaction 3) and the addition reaction of maleimide imino double bond with secondary amine (Reaction 2) to form a cured product of network cross-linking, the reaction is as follows: Reaction 1

The present invention provides a thermosetting resin whose bismaleimide has low solubility in a solvent and poor compatibility with a diamine compound, and cannot be directly mixed and hardened for use. However, it can be dissolved in methyl ethyl ester through a prepolymerization reaction. It is easy to use in solvents such as methyl ketone and toluene. The bismaleimide in the cured product provides high glass transition temperature and low expansion coefficient for the rigid chain. The diamine compound contains flexible segments and some flexible segments. Adjust the segment structure according to the proportion to provide appropriate elasticity, dielectric properties, etc. The cured product has a network cross-linked structure, which can also reduce the expansion coefficient. The molecular structure of the diamine compound copolymerized with bismaleimide is very It is suitable for narrow-line FCCSP and PoP packaging materials, and solves the concerns about the decrease in strength after the wafer is thinned. It can also be used for prepregs, coating materials, film materials, etc. of high-frequency substrates.

The invention provides a thermosetting resin, which is obtained by the reaction of a diamine compound with bismaleimide. The bismaleimide includes: bis (cisbuteneiminophenyl) ether, and bis (cisbutene Eneiminephenyl) methane, bis (cisbuteneiminophenyl) sulfone, bis (cisbuteneiminophenyl) sulfonium, Bis (3-ethyl-5-methyl-4-cis-butenefluorenimidephenyl) methane, bis (3-methyl-5-methyl-4-cisbutenefluorenimidephenyl) methane, Bis (3-ethyl-5-ethyl-4-cis butylideneiminephenyl) methane, bis (cis butylideneimine) m-benzene, bis (cis butylideneimine) p-benzene, di (Cisbuteneimine) o-benzene, bis (cisbuteneimide) toluene, bis (cisbuteneimide) biphenyl, bis (cisbuteneimide) methane, bis (cisbuteneimide) Hydrazone) ethane, bis (maleeneimine) butane, bis (maleeneimine) hexane, bis (maleeneimine) methane, bis (maleimide) ) Octane, bis (maleimide) decane, bis (maleimide) dodecane, one or more of the groups formed, and the like.

The invention provides a thermosetting resin, which is obtained by reacting a diamine compound with bismaleimide. The diamine includes: an amine-terminated polyfluorene imine, an azomethine-containing diamine, and C16 to C44. Divalent hydrocarbon diamines with aliphatic side chains, C16 ~ C44 aliphatic diamines, C16 ~ C44 alicyclic diamines; of which C16 ~ C44 divalent hydrocarbon diamines with aliphatic side chains are unsaturated fatty acids Dimers obtained after reductive amination. The carbon number of unsaturated fatty acids is generally C8 ~ C22. Therefore, dimers containing unsaturated fatty acids can be reductively aminated to obtain C16 ~ C44 dimer amines, of which C36 Diamines known structures include:

加成物、含甲亞(Azomethine)基二胺，所組成組群之一或多種。 The present invention provides a thermosetting resin, which is obtained by the reaction of a diamine compound with bismaleimide. The diamine's Azomethine-containing diamine includes: terephthalaldehyde and C16 ~ C44 are aliphatic. Side chain divalent hydrocarbon diamine adduct, terephthalaldehyde and di (aminocyclohexyl) methane adduct, terephthalaldehyde and 4,4'-methylenebis (2,6-dihexyl) (Cyclohexylamine) adduct, p-phthalaldehyde and 4,4'-methylenebis (2,6-dipentylcyclohexylamine), p-phthalaldehyde and 4,4'-methylenebis ( 2,6-dibutylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylenebis (2,6-diisopropylcyclohexylamine) adduct, terephthalaldehyde Adducts with 4,4'-methylenebis (2,6-diethylcyclohexylamine), terephthalaldehyde and 4,4'-methylenebis (2,6-dimethylcyclohexyl) Amine) adduct, p-phthalaldehyde and 4,4'-methylenebis (2-methyl6-ethylcyclohexylamine) adduct, p-phthalaldehyde and 4,4'-methylene Bis (2-methyl6-isopropylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylenebis (2-methyl6-butylcyclohexylamine) adduct, Terephthalaldehyde and di (aminobenzene) methane adduct, terephthalaldehyde and 4, 4'-methylenebis (2,6-dihexylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis (2,6-dipentylaniline) adduct, p-benzene Addition of formaldehyde and 4,4'-methylenebis (2,6-dibutylaniline), p-phthalaldehyde and 4,4'-methylenebis (2,6-diisopropylaniline) ) Adduct, terephthalaldehyde and 4,4'-methylenebis (2,6-diethylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis (2, 6-dimethylaniline) adduct, p-phthalaldehyde and 4,4'-methylenebis (2-methyl6-ethylaniline) adduct, p-phthalaldehyde and 4,4'- Methylene bis (2-methyl 6-isopropylaniline) adduct, terephthalaldehyde and 4,4'-methylene bis (2-methyl 6-butylaniline) adduct, p- Benzaldehyde

Adduct, Azomethine-containing diamine, one or more groups.

、

，所組成組群之一或多種。其二胺中之端胺基聚醯亞胺合成所使用之二胺單體包括：二(胺基環己基)甲烷、4,4’-亞甲基雙(2,6-二己基環己胺)、4,4’-亞甲基雙(2,6-二戊基環己胺)、4,4’-亞甲基雙(2,6-二丁基環己胺)、4,4’-亞甲基雙(2,6-二異丙基環己胺)、4,4’-亞甲基雙(2,6-二乙基環己胺)、4,4’-亞甲基雙(2,6-二甲基環己胺)、4,4’-亞甲基雙(2-甲基6-乙基環己胺)、4,4’-亞甲基雙(2-甲基6-異丙基環己胺)、4,4’-亞甲基雙(2-甲基6-丁基環己胺)、二(胺基苯)甲烷、4,4’-亞甲基雙(2,6-二己 基苯胺)、4,4’-亞甲基雙(2,6-二戊基苯胺)、4,4’-亞甲基雙(2,6-二丁基苯胺)、4,4’-亞甲基雙(2,6-二異丙基苯胺)、4,4’-亞甲基雙(2,6-二乙基苯胺)、4,4’-亞甲基雙(2,6-二甲基苯胺)、4,4’-亞甲基雙(2-甲基6-乙基苯胺)、4,4’-亞甲基雙(2-甲基6-異丙基苯胺)、4,4’-亞甲基雙(2-甲基6-丁基苯胺)、C32二聚胺、C36二聚胺、C40二聚胺、C44二聚胺、C48二聚胺、C16~C44具脂肪族側鏈之二價烴基二胺，所組成組群之一或多種。其二胺中之端胺基聚醯亞胺合成所使用之二胺單體之莫耳數比二酸酐單體莫耳數為1比0.98~0.50。 The present invention provides a thermosetting resin, and the diacid anhydride monomer used in the synthesis of the amine-terminated polyfluorene imine in the diamine includes:

,

, One or more of the groups. Diamine monomers used in the synthesis of terminal amine polyfluorene imine in its diamine include: bis (aminocyclohexyl) methane, 4,4'-methylenebis (2,6-dihexylcyclohexylamine) ), 4,4'-methylenebis (2,6-dipentylcyclohexylamine), 4,4'-methylenebis (2,6-dibutylcyclohexylamine), 4,4 ' -Methylenebis (2,6-diisopropylcyclohexylamine), 4,4'-methylenebis (2,6-diethylcyclohexylamine), 4,4'-methylenebis (2,6-dimethylcyclohexylamine), 4,4'-methylenebis (2-methyl6-ethylcyclohexylamine), 4,4'-methylenebis (2-methyl) 6-isopropylcyclohexylamine), 4,4'-methylenebis (2-methyl6-butylcyclohexylamine), bis (aminophenyl) methane, 4,4'-methylenebis (2,6-dihexylaniline), 4,4'-methylenebis (2,6-dipentylaniline), 4,4'-methylenebis (2,6-dibutylaniline), 4,4'-methylenebis (2,6-diisopropylaniline), 4,4'-methylenebis (2,6-diethylaniline), 4,4'-methylenebis (2,6-dimethylaniline), 4,4'-methylenebis (2-methyl6-ethylaniline), 4,4'-methylenebis (2-methyl6-isopropyl) Aniline), 4,4'-methylenebis (2-methyl6-butylaniline), C32 dimer, C36 dimer, C40 dimer, C44 dimer, C48 dimer, C16 ~ C44 Divalent hydrocarbon diamine with aliphatic side chain, one or more groups. The mole number of the diamine monomer used in the synthesis of the terminal amine-based polyfluorene imine in the diamine is 1 to 0.98 to 0.50 than the mole number of the diacid anhydride monomer.

The present invention relates to a thermosetting resin. The solvents used in the synthesis include: benzene, toluene, xylene, mesitylene, metaxylene, cyclohexane, 1-butanol, 2-butanol, isobutanol, acetone, methyl Ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, tetrahydrofuran, methyl isoamyl ketone, cyclopentanone, cyclohexanone, diisobutanone, dioxane, γ-butyrolactone, γ- Valerolactone, γ-caprolactone, β-butyrolactone, β-valerolactone, β-caprolactone, γ-butyrolactone, 3-methylcaprylyl-4-lactone, 4-hydroxy- 3-pentenoic acid γ-lactone, chloroform, dichloromethane, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, n-butyl acetate, diethylene glycol Single or mixed solvents of alcohol monobutyl ether acetate, methoxyethanol, ethoxyethanol, dimethylformamide, dimethylacetamide and the like.

一分子中至少含有有二個N-取代馬來醯亞胺基之馬來醯亞胺化和物，所組成組群之一或多種；(b)難燃劑，其包括：

(c)熱固性樹脂，其係由二胺化合物與雙馬來醯亞胺反應所獲致，其特徵在於分子中至少含有一個如式(一)所示之化學結構殘基：

其中R1、R2、R3、R4為相同或不相同，且表示為氫、甲基、乙基、丙基；雙馬來醯亞胺為：

；二胺化合物為：H₂N-A-NH₂；A選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；X為選自：

、

、C24~C48具脂肪族側鏈之二價烴基，所組成組群之一或多種；B為選自：

所組成組群之一或多種；Y為選自：

C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；Z為選自：

、

、C16~C44具脂肪族側鏈之二價烴基，所組成組群之一或多種；n為選自：1~1000的整數；m為選自：1~1000的整數；p為選自：0~1000的整數； q為選自：1~1000的整。 The present invention provides a thermosetting resin composition. The composition includes at least: ( a ) a compound containing two unsaturated groups, including:

A molecule containing at least two N-substituted maleimide imino groups in one molecule, one or more of the group consisting of; (b) a flame retardant, including:

(c) A thermosetting resin, which is obtained by reacting a diamine compound with bismaleimide, and is characterized in that it contains at least one chemical structure residue represented by formula (1) in the molecule:

R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, methyl, ethyl, and propyl; bismaleimide is:

; The diamine compound is: H ₂ NA-NH ₂ ; A is selected from:

C16 ~ C44 have a divalent hydrocarbon group with an aliphatic side chain, which constitutes one or more groups; X is selected from:

,

, C24 ~ C48 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; B is selected from:

One or more of the groups formed; Y is selected from:

C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; Z is selected from:

,

, C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; p is selected from: An integer from 0 to 1000; q is an integer selected from: 1 to 1000.

一分子中至少含有有二個N-取代馬來醯亞胺基之馬來醯亞胺化和物，所組成組群之一或多種。 The present invention provides a thermosetting resin composition, in which (A) a compound containing two unsaturated groups, which includes:

One molecule contains at least two N-substituted maleimide imino groups and one or more groups.

The present invention provides a thermosetting resin composition, wherein the composition (A) contains two unsaturated groups, and one of the molecules contains at least two N-substituted maleimide imide-based maleimide Compounds include: bis (maleimidephenyl) ether, bis (maleimidephenyl) methane, bis (maleimidephenyl) sulfone, bis (maleimide) imine Phenyl) fluorene, bis (3-ethyl-5-methyl-4-cisbutenefluorenimidephenyl) methane, bis (3-methyl-5-methyl-4-cisbutenefluorenimide) Phenyl) methane, bis (3-ethyl-5-ethyl-4-cisbuteneiminephenyl) methane, bis (cisbuteneimine) m-benzene, bis (cisbuteneimide) ) P-benzene, bis (maleimide) o-benzene, bis (maleimide) toluene, bis (maleimide) biphenyl, bis (maleimide) methane, Di (cisbuteneimide) ethane, di (cisbuteneimide) butane, bis (cisbuteneimide) hexane, bis (cisbuteneimide) methane, bis (cisbuteneimide) Butyleneimine) octane, bis (cisbuteneimine) decane, bis (cisbuteneimide) dodecane, phenylmethanemaleimide, with two to five N -take Of the acyl imino maleic 组合 等。 And other.

s+p≧3、

所組成組群之一或多種。 The present invention provides a thermosetting resin composition, in which (B) a flame retardant, which includes:

s + p ≧ 3,

One or more of the formed groups.

The present invention provides a thermosetting resin composition, which may further contain a hardening accelerator, which includes: azobisisobutyronitrile, azobis ( 2 -isopropyl) butyronitrile, azobisisoheptonitrile, Dibenzamidine oxide, isobutyramine peroxide, diethylammonium peroxide, peroxo ( 2,4 -dichlorobenzidine), peroxo ( 2 -dimethylbenzidine), deca peroxide Dihydrazone, diisopropyl peroxydicarbonate, bis ( 3,5,5 -trimethylhexamidine) peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl dicarbonate peroxide, Dicyclohexyl Dicarbonate, Di ( 4 -tert-butylcyclohexyl) dicarbonate, Di ( 2 -ethylhexyl) peroxydicarbonate, Bis ( 2 -phenylethoxy) peroxydicarbonate Ester), dihexadecyl peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, peracetic acid, tert-butyl pervalerate, tert-pervalerate Hexyl ester, cumene peroxyneodecanoate, t-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl pervalerate, isopropyl Benzene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, di-t-butyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide-alkane Base metal, oxy-alkyl metal, etc.

The present invention provides the use of a thermosetting resin, which is used for the manufacture of build-up boards, adhesives for copper foil, semiconductor construction materials, flexible substrates, cover films, adhesive sheets, sealants, pure adhesive films, soft and hard Bonding board, solder mask ink, high frequency flexible substrate, etc.

The invention provides a use of a thermosetting resin composition, which is used for manufacturing laminated boards, high-frequency substrates, build-up boards, adhesives for copper foil, prepregs, semiconductor packaging materials, IC carrier boards, and automotive boards. Wait.

Example 1 (thermosetting resin P-1)

54.7 g (0.10 mole) of dimer fatty amine (1075 / CRODA / amine value: 205), 5- (2,5-dioxotetrahydrofuran) -3-methyl-3-cyclohexene-1,2- Dicarbonic anhydride (manufactured by B-4400 / DIC) 25.08 g (0.095 mole), 10 g of dimethylacetamide, 100 g of diisobutyl ketone, and 0.01 g of triethylamine are placed in a tube equipped with a mechanical stirring, condensation tube, and drying tube In a four-necked reaction flask with a distillation receiver and nitrogen, the reaction temperature is controlled at 20 ° C to 30 ° C, the reaction is performed for 3 hours, and the temperature is heated to 130 ° C to 180 ° C to azeotropically remove water, and the reaction is performed for 4 hours to remove the solvent under reduced pressure. The amine valence was detected to be 7.4 to obtain an amine-terminated polyfluorene imine. The temperature was lowered to 90 ° C, and 50 g of toluene and bis (3-ethyl-5-methyl-4-cisbutenefluorene imine phenyl) were added. ) 4.42 g (0.010 mole) of methane, reacted at 90 ° C for 10 hours, Michael addition reaction was performed, and di (3-ethyl-5-methyl-4-cis-buteneiminophenyl) methane residue was detected by GPC The amount was 0.15%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-1.

Example 2 (thermosetting resin P-2)

Siloxane diamine (KF-8010 / Shin-Etsu) 86.0 g (0.100 mole), biphenyltetracarboxylic dianhydride 27.93 g (0.095 mole), dimethylacetamide 10 g, diisobutanone 100 g, triethyl 0.01g of amine was placed in a four-necked reaction flask equipped with a mechanical stirrer, condensation tube, drying tube, distillation receiver, and nitrogen. The reaction temperature was controlled at 20 ° C to 30 ° C for 2 hours, and then heated to 130 ° C to 180 ° C. The water was removed by azeotropy at ℃, and the reaction was carried out for 4 hours. The solvent was removed under reduced pressure. The amine value was determined to be 5.4 to obtain an amine-terminated polyimide. The temperature was lowered to 90 ° C. 50 g of toluene and di (3-ethyl Methyl-5-methyl-4-cisbutenylimidephenyl) methane 4.42g (0.010mole), reacted at 90 ° C for 10 hours, and carried out Michael addition reaction to GPC detected the residual amount of bis (3-ethyl-5-methyl-4-cisbutenyliminephenyl) methane as 0.22%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-2.

Example 3 (thermosetting resin P-3)

4,4'-methylenebis (2-methyl6-ethylaniline) 14.1 g (0.05 mole), bis (aminocyclohexyl) methane 10.5 g (0.05 mole), siloxane tetraacid dianhydride (DMS-Z21 / Gelest, Ltd.) '66.5g (0.095mole), dimethylacetamide 10g, diisobutyl ketone 100g, 0.01g triethylamine, placed equipped with mechanical stirrer, condenser, drying tube, distillation In a four-necked reaction flask with a receiver and a nitrogen gas, the reaction temperature is controlled at 20 ° C to 30 ° C, and the reaction is performed for 2 hours, and then heated to 130 ° C to 180 ° C to azeotropically remove water, and the reaction is performed for 4 hours to remove the solvent under reduced pressure. The amine valence was determined to be 6.5, and an amine-terminated polyfluorene imine was obtained. The temperature was lowered to 90 ° C, 50 g of toluene and bis (3-ethyl-5-methyl-4-cis-butenefluoreniminephenyl) were added. 4.42 g (0.010 mole) of methane, reacted at 90 ° C for 10 hours, Michael addition reaction was performed, and di (3-ethyl-5-methyl-4-cis-buteneiminophenyl) methane residue was detected by GPC At 0.10%, the solvent was removed under reduced pressure to obtain a thermosetting resin P-3.

Example 4 (Thermosetting resin P-4)

(PPHT/日本精化製)43.32g(0.095mole) 、二甲基乙醯胺10g、二異丁酮100g、三乙胺0.01g，反應溫度控制在20℃~30℃，反應2小時，之後加熱至130℃~180℃共沸去除水份，反應4小時，以減壓脫除溶劑，檢測其胺價為1.8，得到端胺基聚醯亞胺，將溫度降至90℃，加入甲苯50g及二(3-乙基-5-甲基-4-順丁烯醯亞胺苯基)甲烷4.42g(0.010mole)，以90℃反應10小時，進行Michael加成反應，以GPC檢測二(3-乙基-5-甲基-4-順丁烯醯亞胺苯基)甲烷殘量為0.06%，以減壓脫除溶劑，得到熱固性樹脂P-4。 13.4 g (0.10 mole) of terephthalaldehyde, 114.2 g (0.20 mole) of dimer fatty amine (1075 / CRODA / amine price: 205), and 50 g of xylene are placed in a tube equipped with a mechanical stirrer, a condensation tube, and a drying tube. In a four-necked reaction flask with a distillation receiver and nitrogen, the reaction temperature is controlled at 80 ° C to 90 ° C, and the reaction is carried out for 12 hours. The solvent is removed under reduced pressure to obtain an azomethine-containing diamine. 90.5, added

(PPHT / made in Japan) 43.32g (0.095mole), 10g of dimethylacetamide, 100g of diisobutanone, 0.01g of triethylamine, the reaction temperature is controlled at 20 ° C ~ 30 ° C, and the reaction is performed for 2 hours, after that Heat to 130 ° C ~ 180 ° C to remove water by azeotropy, react for 4 hours, remove the solvent under reduced pressure, and check its amine value to be 1.8 to obtain amine-terminated polyimide. Reduce the temperature to 90 ° C and add 50g of toluene. And 4.42 g (0.010 mole) of bis (3-ethyl-5-methyl-4-cisbutenyliminephenyl) methane, reacted at 90 ° C for 10 hours, carried out Michael addition reaction, and detected di ( The residual amount of 3-ethyl-5-methyl-4-cisbuteneiminophenyl) methane was 0.06%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-4.

Example 5 (thermosetting resin P-5)

13.4 g (0.10 mole) of p-xylylene dialdehyde, 172.0 g (0.200 mole) of siloxane diamine (KF-8010 / Shin-Etsu), and 50 g of xylene are placed in a machine equipped with a mechanical stirring, condensation tube, drying tube, and distillation In a four-necked reaction flask with a receiver and a nitrogen gas, the reaction temperature is controlled at 80 ° C to 90 ° C, and the reaction is performed for 12 hours. The solvent is removed under reduced pressure to obtain an azomethine-containing diamine. The amine value is 62.3. Add 28.5 g of 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA-100 / Shinnippon Physicochemical) 0.095mole), 10 g of dimethylacetamide, 100 g of diisobutyl ketone, and 0.01 g of triethylamine. The reaction temperature is controlled at 20 ° C to 30 ° C for 2 hours, and then heated to 130 ° C to 180 ° C to remove water azeotropically. Parts, react for 4 hours, remove the solvent under reduced pressure, and check its amine value to be 3.9 to obtain amine-terminated polyfluorene imine. Reduce the temperature to 90 ° C, add 50 g of toluene and bis (3-ethyl-5-formaldehyde) 4.44-g (0.010 mole) of methyl-4-cis-buteneiminophenyl) methane, reacted at 90 ° C for 10 hours, carried out Michael addition reaction, and detected di (3-ethyl-5-methyl-4) by GPC -Cis-buteneiminophenyl) methane residue is 0.06%, the solvent is removed under reduced pressure to obtain Thermosetting resin P-5.

Example 6 (Thermosetting resin P-6)

13.4 g (0.10 mole) of terephthalaldehyde, 4,4'-methylenebis (2-methyl 6- Ethylaniline) 28.2g (0.10mole), bis (aminocyclohexyl) methane 21.0g (0.10mole), xylene 50g, put in a mechanical stirrer, condensation tube, drying tube, distillation receiver, nitrogen 4 In the reaction flask, the reaction temperature is controlled at 80 ° C to 90 ° C, and the reaction is performed for 12 hours. The solvent is removed under reduced pressure to obtain a methylamine (Azomethine) -containing diamine. The amine valence is 191. Siloxane tetraacid is added. 66.5 g (0.095 mole) of dianhydride (manufactured by DMS-Z21 / Gelest), 10 g of dimethylacetamide, 100 g of diisobutanone, and 0.01 g of triethylamine. The reaction temperature is controlled at 20 ° C to 30 ° C, and the reaction is performed for 2 hours. Then, it was heated to 130 ° C ~ 180 ° C to remove water by azeotropy. After 4 hours of reaction, the solvent was removed under reduced pressure. The amine value was determined to be 4.7 to obtain an amine-terminated polyimide. Reduce the temperature to 90 ° C and add 50g of toluene and 4.42g (0.010mole) of bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, reacted at 90 ° C for 10 hours, carried out Michael addition reaction, and detected by GPC The residual amount of bis (3-ethyl-5-methyl-4-cisbuteneiminophenyl) methane was 0.07%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-6.

Example 7 (thermosetting resin P-7)

13.4 g (0.10 mole) of terephthalaldehyde, 114.2 g (0.20 mole) of dimer fatty amine (1075 / CRODA / amine price: 205), and 50 g of xylene are placed in a tube equipped with a mechanical stirrer, a condensation tube, and a drying tube. In a four-necked reaction flask with a distillation receiver and nitrogen, the reaction temperature is controlled at 80 ° C to 90 ° C, and the reaction is carried out for 12 hours. The solvent is removed under reduced pressure to obtain an azomethine-containing diamine. 90.6, 50 g of methyl ethyl ketone and 88.4 g (0.20 mole) of bis (3-ethyl-5-methyl-4-cisbutenyliminephenyl) methane were added, and the reaction was carried out at 90 ° C. for 10 hours to perform a Michael addition reaction. The residual amount of bis (3-ethyl-5-methyl-4-cisbutenyliminephenyl) methane was detected by GPC to be 0.83%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-7.

Example 8 (Thermosetting resin P-8)

Add 13.4 g (0.10 mole) of terephthalaldehyde, siloxane diamine (KF-8010 / Shin-Etsu 86.0 g (0.100 mole), 21.0 g (0.10 mole) of bis (aminocyclohexyl) methane, 50 g of xylene, and placed in a four-port reaction equipped with mechanical stirring, condensation tube, drying tube, distillation receiver, nitrogen In the bottle, the reaction temperature was controlled at 80 ° C to 90 ° C, and the reaction was carried out for 12 hours. The solvent was removed under reduced pressure to obtain an azomethine-containing diamine. The amine valence was 96.1. 50 g of methyl ethyl ketone and 2 (3 -Ethyl-5-methyl-4-cis-buteneiminophenyl) methane 88.4 g (0.20 mole), reacted at 90 ° C for 10 hours, Michael addition reaction was performed, and di (3-ethyl The residual amount of -5-methyl-4-cisbuteneiminophenyl) methane was 0.86%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-8.

Example 9 (thermosetting resin P-9)

Dimerized fatty amine (1075 / CRODA / amine value: 205) 57.1 g (0.10 mole), 50 g of methyl ethyl ketone and bis (3-ethyl-5-methyl-4-cis butylideneimine phenyl) 88.4 g (0.20 mole) of methane was placed in a four-necked reaction flask equipped with a mechanical stirrer, condensation tube, drying tube, distillation receiver, and nitrogen. The reaction temperature was controlled at 80 ° C to 90 ° C, and the reaction was performed at 90 ° C for 10 hours. The Michael addition reaction was performed, and the residual amount of bis (3-ethyl-5-methyl-4-cis-buteneiminophenyl) methane was determined by GPC to be 1.20%. The solvent was removed under reduced pressure to obtain a thermosetting resin P. -9.

Examples 10 to 18

Examples 10 to 18 are as follows: 10 parts by weight of each of the thermosetting resins P-1 to P9 and 10 parts by weight of toluene are stirred and dissolved to form a glue solution, and the glue solution is coated on a polyimide film having a thickness of 12.5 μm. The dry thickness of the coating layer is 25 μm. The coated polyimide film is dried at 50 ° C. for 10 minutes and 60 ° C. for 30 minutes to obtain a cover film. The cover film is adhered to a copper foil having a thickness of 35 μm and hot-pressed. 200 ° C / 40Kg / 40 minutes, measure its adhesive strength; apply the glue on the PET film, dry at 50 ° C for 10 minutes, dry at 60 ° C for 30 minutes, bake at 150 ° C for 3 hours, and finally cure at 200 ° C for 3 hours. The cured product having a film thickness of 0.2 mm was obtained after 1 hour, and its glass transition temperature, dielectric constant, dielectric loss, folding resistance, and adhesive strength were measured. The data are shown in Table 1.

Comparative Example 1

10 parts by weight of styrene-based polyphenylene ether (manufactured by OPE-St-2200 / MGC ) and 10 parts by weight of toluene were stirred to dissolve into a glue solution, and the glue solution was coated on a polyimide film having a thickness of 12.5 μm, and coated with The dry thickness of the layer was 25 μm. The coated polyimide film was dried at 50 ° C. for 10 minutes and 60 ° C. for 30 minutes to obtain a cover film. The cover film was adhered to a 35 μm-thick copper foil and hot-pressed 200 ℃ / 40Kg / 40 minutes, measure its adhesive strength; apply glue on PET film, dry at 50 ℃ for 10 minutes, dry at 60 ℃ for 30 minutes, bake at 150 ℃ for 3 hours, and finally cure at 200 ℃ for 3 hours To obtain a cured product with a film thickness of 0.2 mm, the glass transition temperature, dielectric constant, dielectric loss, folding resistance, and bonding strength were measured. The data are shown in Table 1.

Glass transition temperature (Tg): Measured with TMA manufactured by TA Corporation.

Dielectric constant (Dk): It was measured at a frequency of 1 GHz using an LCR Meter manufactured by Agilent Corporation.

Dielectric loss (Df): It was measured at a frequency of 1 GHz using a resonant cavity manufactured by Agilent.

Adhesive strength: The cover film was adhered to a copper foil with a thickness of 35 μm, and hot-pressed at 200 ° C / 40Kg / 40 minutes. The test piece was cut into a length of 10 cm and a width of 1 cm. The copper foil layer was pulled upward in a vertical direction at a speed of 50 mm / min. The unit is N / cm.

Folding resistance: The cured product with a film thickness of 0.2mm is folded in half at an angle of 180 degrees to check the appearance.

○ indicates no creases

△ indicates crease

X indicates a crack

Examples 19 ~ 27

Examples 19 to 27 are as follows: 10 parts by weight of each of thermosetting resins P-1 to P-9, 10 parts by weight of a compound containing two unsaturated groups, 4 parts by weight of a flame retardant, and 20 parts by weight of toluene are used to make a glue. Liquid, impregnated 2116 glass fiber cloth with glue, and dried it at 175 ° C for 2 ~ 15 minutes to make a semi-cured prepreg. Then four prepregs were laminated, one 0.5 oz copper on each side. The foil is then hot-pressed under the conditions that the temperature is increased to 230 ° C at a temperature of 1 to 3 ° C / min, and the heat is pressed at a temperature of 8 to 15 kg / cm2 for 180 minutes at this temperature, thereby obtaining a laminated board and measuring the glass thereof. The data of transfer temperature, dielectric loss, dielectric constant, flame resistance, tear strength, and flexural modulus are shown in Table 2.

Comparative Example 2

10 parts by weight of styryl polyphenylene ether (manufactured by OPE-St-2200 / MGC), 10 parts by weight of a compound containing two unsaturated groups, 4 parts by weight of a flame retardant, and 20 parts by weight of toluene were made into a glue solution. 2116 The glass fiber cloth is impregnated with glue and dried at 175 ° C for 2 to 15 minutes to make a prepreg in a semi-cured state. Then, four prepregs are laminated, and a 0.5 oz copper foil is placed on each of the upper and lower sides. Hot pressing under the conditions of heating at a temperature of 1 ~ 3 ℃ / min to 230 ℃, and hot pressing at a temperature of 8 ~ 15kg / cm2 for 180 minutes at this temperature, thereby obtaining a laminated board, measuring its glass transition temperature, medium The data of electrical loss, dielectric constant, flame resistance, tear strength, and flexural modulus are shown in Table 2.

Glass transition temperature (Tg): After removing the copper foil from the laminated board, it was measured with TMA manufactured by TA Corporation.

Dielectric constant (Dk): After removing the copper foil from the laminated board, it was measured at a frequency of 1 GHz using an LCR Meter manufactured by Agilent Corporation.

Dielectric loss (Df): After removing the copper foil from the laminated board, a cavity / network analyzer manufactured by Agilent was used. Measured at a frequency of 1 GHz.

Flame retardancy: After removing the copper foil from the laminated board, it is measured by UL-94V vertical combustion method.

Tear strength: The adhesion of the copper foil layer to the laminated board. The force required to vertically tear the copper foil from the surface of the board with a 1/8 inch wide copper unit, in pounds per inch.

Flexural modulus: According to JIS-K6911 method, Shimadzu AG-X universal testing machine is used.

BMI-5000：二(3-乙基-5-甲基-4-順丁烯醯亞胺苯基)甲烷(Designer molecules製)。

BMI-5000: bis (3-ethyl-5-methyl-4-cisbuteneiminophenyl) methane (made by Designer molecules).

From Table 1, it can be seen that the thermosetting resins P-1 to 9 of Examples 1 to 9 of the present invention have a dielectric constant (Dk) of 2.9 or less and a dielectric loss (Df) of 0.0034 or less. The vinyl polyphenylene ether is better. Therefore, the present invention provides a thermosetting resin, which meets the requirements of low dielectric properties, high adhesion, and folding resistance of the next-generation high-frequency flexible substrate. The cured product of the thermosetting resin composition of 27 has a flame retardancy of V-0, a glass transition temperature of 190 to 254 ° C, a dielectric loss (Df) of 0.0032 or less, and a dielectric constant (Dk) of 2.4 or less, which is better than The cured product of the conventional vinyl polyphenylene ether composition of Comparative Example 2 also has better tear strength and flexural modulus than the cured product of the vinyl polyphenylene ether composition of Comparative Example 2. Therefore, the present invention provides a thermosetting resin. The composition meets the requirements of low dielectric properties, flame resistance, high tear strength, and high flexural modulus of next-generation high-frequency substrates and semiconductor packaging substrates.

The present invention provides the use of a thermosetting resin, which is used for the manufacture of build-up boards, adhesives for copper foil, semiconductor construction materials, flexible substrates, cover films, adhesive sheets, sealants, pure adhesive films, soft Hard bonding board, solder mask, high frequency flexible substrate, etc. The invention provides the use of a thermosetting resin composition, which is used for manufacturing laminated boards, high-frequency substrates, build-up boards, adhesives for copper foil, prepregs, semiconductor structural materials, IC substrates, and automotive applications. Board, etc.

The present invention has been described in conjunction with the above specific embodiments and comparative examples, and those skilled in the art will be able to make various changes based on the above description without limiting the scope of patent application of the present invention.

Claims (4)

A thermosetting resin, which is obtained by reacting a diamine compound with bismaleimide, and is characterized in that it contains at least one chemical structure residue represented by formula (1) in the molecule:

R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, methyl, ethyl, and propyl; bismaleimide is:

; The diamine compound is: H ₂ NA-NH ₂ ; A is selected from:

C16 ~ C44 have a divalent hydrocarbon group with an aliphatic side chain, which constitutes one or more groups; X is selected from:

,

, C24 ~ C48 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; B is selected from:

One or more of the groups formed; Y is selected from:

C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; Z is selected from:

,

, C16 ~ C4-4 divalent hydrocarbon group with aliphatic side chain, one or more of the group; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; p is selected From: an integer from 0 to 1000; q is an integer selected from: 1 to 1000. A thermosetting resin composition comprising at least: ( a ) a compound containing two unsaturated groups, including:

A molecule containing at least two N-substituted maleimide imino groups in one molecule, one or more of the group consisting of; (b) a flame retardant, including:

(c) A thermosetting resin, which is obtained by reacting a diamine compound with bismaleimide, and is characterized in that it contains at least one chemical structure residue represented by formula (1) in the molecule:

R1, R2, R3, and R4 are the same or different, and are represented by hydrogen, methyl, ethyl, and propyl; bismaleimide is:

; The diamine compound is: H ₂ NA-NH ₂ ; A is selected from:

C16 ~ C44 have a divalent hydrocarbon group with an aliphatic side chain, which is one or more of the group; X is selected from:

,

, C24 ~ C48 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; B is selected from:

One or more of the groups formed; Y is selected from:

C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; Z is selected from:

,

, C16 ~ C44 are divalent hydrocarbon groups with aliphatic side chains, which constitute one or more groups; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; p is selected from: An integer from 0 to 1000; q is an integer selected from: 1 to 1000. A use of thermosetting resins such as the scope of application for patent No. 1 is used for the manufacture of build-up boards, adhesives for copper foil, semiconductor packaging materials, flexible substrates, cover films, adhesive sheets, sealants, pure Adhesive film, flexible and rigid board, solder mask, high frequency flexible substrate, etc. A use of a thermosetting resin composition such as the scope of patent application No. 2 is used for manufacturing laminated boards, high-frequency substrates, build-up boards, adhesives for copper foil, prepregs, semiconductor construction materials, IC carriers Boards, automotive boards, etc.