TWI582136B - Thermosetting resin and its composition, use - Google Patents

Description

Thermosetting resin and its composition and use

The present invention provides a thermosetting resin and a composition thereof, the composition comprising at least: (a) a compound containing two unsaturated groups, (b) a flame retardant, and (c) a thermosetting resin which is added to the buildup layer Adhesive for sheet and copper foil, semiconductor package, flexible substrate, cover film, adhesive sheet, sealant, pure film, soft and hard bonding board, solder resist ink, high frequency flexible substrate, high frequency substrate, Additive layer, adhesive for copper foil, prepreg, IC carrier, vehicle board, etc.

With the advancement of communication electronic technology, the signal transmission of large computers, mobile communications, base stations, servers, routers, and intelligent transmission systems (ITS) of smart cars is developing toward high frequency and high speed, among which low dielectric resin materials Become a key material in high-speed transmission technology, its low dielectric constant (Dk) will affect the speed of signal transmission, low dielectric loss (Df) will affect the quality of signal transmission; mobile communication device trend is high speed and light and thin, high The density substrate replaces the conventional substrate, the substrate is extremely thinned, multilayered, and high-density, and the semiconductor is embedded toward the interior. The substrate material and the packaging material are required to have higher characteristics such as glass transition temperature and low dielectric property, and need to be further advanced. Properties such as properties and modulus of elasticity, in which the modulus of elasticity and the coefficient of expansion affect the warpage and elastic modulus of the semiconductor package substrate, which directly affects the toughness of the substrate and the reliability of the hole.

Patent Document CN102993491-A discloses a thermosetting resin composition which improves the metal bond strength of a phenolic polyphenylene ether with a butadiene polymer having a Df of 0.003 or more and a Dk of 3.2 or more.

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

Known technology Among the resin materials, only vinyl polyphenylene ether (TWI250995) has better dielectric properties (Dk about 2.6, Df about 0.003), glass transition temperature can reach about 180 ° C, but vinyl polyphenylene ether in Under the condition of low dielectric properties, it is technically difficult to simultaneously increase the glass transition temperature and elastic modulus, or the toughness, folding resistance and adhesion to the polyimide film and copper foil of vinyl polyphenylene ether. There is still much room for improvement.

One problem to be solved by the present invention lies in the prior art problem in that although polyphenylene ether and polytetrafluoroethylene can meet the industrial requirements of low dielectric loss Df (1 GHz) of 0.004 or less, polyphenylene ether itself is too brittle. The folding endurance and the subsequent strength are not good, and the PTFE is difficult to process. The characteristics of the two are not sufficient for the flexible substrate, which cannot meet the expectations and needs of the industry. The second is the problem of the prior art, which is widely used. The polyphenylene ether resin and the cured product of the high-frequency substrate have a low dielectric loss (Df) and a low dielectric constant (Dk), but the glass transition temperature is lower than 180 ° C, and the substrate orientation is extremely thin. In order to solve the problem of heat dissipation, it is necessary to increase the temperature of glass transition, in order to solve the problem of heat dissipation, and to increase the tear strength and the bending modulus, in order to meet the requirements of the technology of multi-layered, high-density semiconductors. Requirements for next generation high frequency substrates and semiconductor packaging materials.

The technical means for solving the problem of the present invention is to provide a thermosetting resin obtained by reacting a diamine compound with bismaleimide, characterized in that the molecule contains at least one chemical structure residue as shown in formula (I). base: Wherein R1 , R2 , R3 and R4 are the same or different and are represented by hydrogen, methyl, ethyl or propyl; the diamine compound is: H ₂ NA-NH ₂ ; A is selected from the group consisting of: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; X is selected from the group consisting of: , , C24~C48 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; B is selected from the group consisting of: One or more of the group consisting of; Y is selected from: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; Z is selected from the group consisting of: , And C16-C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; and p is selected from the group consisting of: An integer from 0 to 1000; q is selected from the group consisting of: 1 to 1000.

The present invention provides a thermosetting resin composition comprising at least: (a) a compound containing two unsaturated groups, which comprises: One or more of the group consisting of two N-substituted maleimine groups, and one or more of the groups; (b) a flame retardant comprising: (c) a thermosetting resin obtained by reacting a diamine compound with bismaleimide, characterized in that the molecule contains at least one chemical structure residue as shown in formula (I): Wherein R1 , R2 , R3 and R4 are the same or different and are represented by hydrogen, methyl, ethyl or propyl; the diamine compound is: H ₂ NA-NH ₂ ; A is selected from the group consisting of: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; X is selected from the group consisting of: , , C24~C48 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; B is selected from the group consisting of: One or more of the group consisting of; Y is selected from: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; Z is selected from the group consisting of: , And C16-C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; and p is selected from the group consisting of: An integer from 0 to 1000; q is selected from the group consisting of: 1 to 1000.

The present invention provides a use of a thermosetting resin for producing a build-up plate, an adhesive for a copper foil, a semiconductor package, a flexible substrate, a cover film, an adhesive sheet, a sealant, a pure film, and a soft Hard bonding board, solder resist ink, high frequency flexible substrate, etc.

The present invention provides a use of a thermosetting resin composition for producing a laminate, a high-frequency substrate, a build-up plate, an adhesive for a copper foil, a prepreg, a semiconductor package, an IC carrier, and a vehicle. Board and so on.

One of the effects of the prior art is that although vinyl polyphenylene ether and polytetrafluoroethylene can meet the industrial requirements of low dielectric loss Df (1 GHz) of 0.003 or less, polyphenylene ether itself is too brittle, folding resistance and adhesion strength. Poor, PTFE is not easy to process, and the properties of the two are not sufficient for the flexible substrate, which cannot meet the expectations and needs of the industry. The present invention provides a thermosetting resin with low dielectric properties and high adhesion. The properties such as folding resistance meet the requirements of the next-generation high-frequency flexible substrate; the second is the polyphenylene ether resin and the cured product of the composition, which have a low dielectric loss (Df) and a low dielectric constant. (Dk), but the glass transition temperature is below 180 ° C. The present invention provides a cured product of a composition which has flame retardancy, low dielectric loss (Df), low dielectric constant (Dk), and higher glass transition. The tear strength and flexural modulus can meet the requirements of the next generation of high-frequency substrates and semiconductor packaging materials and the industry's earnest expectations.

The present invention provides a thermosetting resin obtained by reacting a diamine compound with bismaleimide, characterized in that the molecule contains at least one chemical structure residue as shown in formula (I): Wherein R1 , R2 , R3 and R4 are the same or different and are represented by hydrogen, methyl, ethyl or propyl; the diamine compound is: H ₂ NA-NH ₂ ; A is selected from the group consisting of: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; X is selected from the group consisting of: , , C24~C48 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; B is selected from the group consisting of: One or more of the group consisting of; Y is selected from: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; Z is selected from the group consisting of: , And C16-C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; and p is selected from the group consisting of: An integer from 0 to 1000; q is selected from the group consisting of: 1 to 1000.

The present invention provides a thermosetting resin which is subjected to a Michael addition reaction (reaction 1) of a diamine compound and bismaleimide at 50 ° C to 180 ° C to form a linear structure, and may also have a small portion of Malayan The side reaction of the addition of an amine double bond with a secondary amine (Reaction 2), the maleimine double bond is opened when solidified at 180 ° C to 230 ° C, and the free radical of the maleimine group is carried out. The polyreaction (reaction 3) and the maleimine double bond and the secondary amine addition reaction (reaction 2) form a network crosslinked cured product, and the reaction is as follows:

The invention provides a thermosetting resin, wherein the bismaleimide has low solubility in a solvent and has poor compatibility with a diamine compound, cannot be directly mixed and hardened, but can be dissolved in methyl ethyl group by prepolymerization. It is easy to use in solvents such as ketone and toluene. In its solidified product, bismaleimide provides high glass transition temperature and low expansion coefficient for rigid chain. Diamine compound contains soft segment and partial soft segment. Adjusting the structure of the chain according to the ratio, providing appropriate elastic modulus, dielectric properties, etc., the cured product has a network cross-linked structure, and can also reduce the expansion coefficient. The molecular structure of the diamine compound and the bismaleimide copolymer is very It is suitable for packaging materials with narrow line FCCSP and PoP, and can solve the problem of thinning of the wafer and then reducing the strength. It can also be used for prepreg, coating material, film material, etc. of high frequency substrate.

The present invention provides a thermosetting resin obtained by reacting a diamine compound with bismaleimide, the bismaleimide comprising: bis(cis-butenylene phenyl) ether, bis (cis-butane) Iridium imine phenyl)methane, bis(cis-butenylene phenyl) sulfone, bis(cis-butenylene phenyl) fluorene, bis(3-ethyl-5-methyl-4-cis Butenoindolyl phenyl)methane, bis(3-methyl-5-methyl-4-cis-buteneniminephenyl)methane, bis(3-ethyl-5-ethyl-4-cis Butylene ylidene phenyl)methane, bis(succinimide)m-phenylene, bis(cis-succinimide)-p-benzene, bis(cis-s-imine)-o-benzene, bis(cis-butene) Iridium imine) toluene, bis(succinimide)biphenyl, bis(cis-succinimide)methane, bis(n-butenenimine)ethane, bis(cis-butenylene imine) Butane, bis(n-butenenimine)hexane, bis(n-butenenimine)methane, bis(cis-succinimide)octane, bis(cis-butenyleneimide)decane And bis(succinimide)dodecane, one or more of the group formed.

The invention provides a thermosetting resin obtained by reacting a diamine compound with a bismaleimide, the diamine comprising: a terminal amine polyimine, an Azomethine-based diamine, a C16-C44 a divalent hydrocarbyl diamine having an aliphatic side chain, a C16-C44 aliphatic diamine, a C16-C44 alicyclic diamine; wherein the C16-C44 divalent hydrocarbyl diamine having an aliphatic side chain is an unsaturated fatty acid After the reductive amination of the dimer, the carbon number of the unsaturated fatty acid is generally C8~C22, so the dimer of the unsaturated fatty acid can be reductively aminated to obtain C16~C44 dimeric amine, wherein C36 Known structures of dimeric amines include:

The present invention provides a thermosetting resin obtained by reacting a diamine compound with bismaleimide, and the Azomethine-based diamine of the diamine includes: terephthalaldehyde and C16-C44 having an aliphatic group Bivalent hydrocarbon diamine adducts of side chains, terephthalaldehyde and bis(aminocyclohexyl)methane adducts, terephthalaldehyde and 4,4'-methylenebis(2,6-dihexyl) Cyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylenebis(2,6-dipentylcyclohexylamine), terephthalaldehyde and 4,4'-methylene double ( 2,6-Dibutylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylenebis(2,6-diisopropylcyclohexylamine) adduct, terephthalaldehyde And 4,4'-methylenebis(2,6-diethylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylenebis(2,6-dimethylcyclohexane Amine) adduct, terephthalaldehyde and 4,4'-methylenebis(2-methyl 6-ethylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylene Bis(2-methyl 6-isopropylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylenebis(2-methyl 6-butylcyclohexylamine) adduct, Terephthalaldehyde and bis(aminophenyl)methane adduct, terephthalaldehyde and 4, 4'-methylenebis(2,6-dihexylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis(2,6-dipentylaniline) adduct, p-benzene Diformaldehyde and 4,4'-methylenebis(2,6-dibutylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis(2,6-diisopropylaniline) Adduct, terephthalaldehyde and 4,4'-methylenebis(2,6-diethylaniline) adduct, terephthalaldehyde and 4,4'-methylene double (2, 6-Dimethylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis(2-methyl 6-ethylaniline) adduct, terephthalaldehyde and 4,4'- Methylene bis(2-methyl 6-isopropylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis(2-methyl 6-butylaniline) adduct, pair Benzaldehyde and The adduct, one or more of the group consisting of Azomethine-based diamines.

The invention provides a thermosetting resin, wherein the dianhydride monomer used in the synthesis of the terminal amine polyimine in the diamine comprises: , , one or more of the group. The diamine monomer used in the synthesis of the terminal amine polyimine in the diamine includes: 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'-methylene double (2,6-Dimethylcyclohexylamine), 4,4'-methylenebis(2-methyl 6-ethylcyclohexylamine), 4,4'-methylenebis(2-methyl 6-isopropylcyclohexylamine), 4,4'-methylenebis(2-methyl 6-butylcyclohexylamine), bis(aminophenyl)methane, 4,4'-methylene double (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,-methylene double (2,6-dimethylaniline), 4,4,-methylenebis(2-methyl 6-ethylaniline), 4,4'-methylenebis(2-methyl 6-isopropyl Aniline), 4,4'-methylenebis(2-methyl 6-butylaniline), C32 diamine, C36 diamine, C40 diamine, C44 diamine, C48 diamine, C16 ~C44 A divalent hydrocarbyl diamine having an aliphatic side chain, one or more of which is composed of a group. The molar ratio of the diamine monomer used in the synthesis of the terminal amine polyimine in the diamine is 1 to 0.98 to 0.50.

The invention relates to a thermosetting resin, wherein the solvent used for the synthesis comprises: benzene, toluene, xylene, mesitylene, trimellitic acid, 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-methyloctyl-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 monobutyl ether acetate, methoxyethanol, ethoxyethanol, dimethyl A single or mixed solvent of guanamine, dimethylacetamide or the like.

The present invention provides a thermosetting resin composition comprising at least: (a) a compound containing two unsaturated groups, which comprises: One or more of the group consisting of two N-substituted maleimine groups, and one or more of the groups; (b) a flame retardant comprising: (c) a thermosetting resin obtained by reacting a diamine compound with bismaleimide, characterized in that the molecule contains at least one chemical structure residue as shown in formula (I): formula (I) Wherein R1 , R2 , R3 and R4 are the same or different and are represented by hydrogen, methyl, ethyl or propyl; the diamine compound is: H ₂ NA-NH ₂ ; A is selected from the group consisting of: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; X is selected from the group consisting of: , , C24~C48 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; B is selected from the group consisting of: One or more of the group consisting of; Y is selected from: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; Z is selected from the group consisting of: , And C16-C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; and p is selected from the group consisting of: An integer from 0 to 1000; q is selected from the group consisting of: 1 to 1000.

The present invention provides a thermosetting resin composition in which (A) a compound containing two unsaturated groups, which comprises: One or more of the group consisting of at least two N-substituted maleimine groups of maleimine.

The present invention provides a thermosetting resin composition in which (A) a compound containing two unsaturated groups, wherein one of the molecules contains at least two N-substituted maleimine-based maleimine The compound includes: bis(cis-butenylene phenyl) ether, bis(cis-butenylene) Amine phenyl)methane, bis(cis-butenylene phenyl) sulfone, bis(cis-butenylene phenyl) hydrazine, bis(3-ethyl-5-methyl-4-cis-butenylene) Iminophenyl)methane, bis(3-methyl-5-methyl-4-cis-buteneniminephenyl)methane, bis(3-ethyl-5-ethyl-4-cis-butenylene Iminophenyl)methane, di(n-butenenimine)-m-benzene, bis(cis-s-imide)-p-benzene, bis(cis-s-imine)-o-benzene, bis(cis-butenylene) Amine) toluene, di(n-butenenimine)biphenyl, di(n-butenenimine)methane, bis(n-butenenimine)ethane, di(cis-butenyleneimine)butane , bis(succinimide) hexane, bis(cis-succinimide)methane, bis(cis-succinimide)octane, bis(cis-succinimide) decane, two ( Doxamethylene imine) dodecane, phenylmethane maleimide, a compound having two to five N-substituted maleimine groups, and the like.

The present invention provides a thermosetting resin composition, wherein the composition (B) is a flame retardant, comprising: One or more of the groups formed.

The present invention provides a thermosetting resin composition, which may further comprise a hardening accelerator, which comprises: azobisisobutyronitrile, azobis( 2 -isopropyl)butyronitrile, azobisisoheptanenitrile, Benzoyl sulfonium oxide, isobutyl hydrazine peroxide, diethyl hydrazine peroxide, peroxy ( 2,4 -dichlorobenzhydrazide), peroxy ( 2 -dimethylbenzhydrazide), peroxidized Diterpene, diisopropyl peroxydicarbonate, bis( 3,5,5 -trimethylhexyl) peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl peroxydicarbonate, Dicyclohexyl oxydicarbonate, bis( 4 -tert-butylcyclohexyl)dicarbonate, bis( 2 -ethylhexyl)peroxydicarbonate, bis( 2 -phenylethoxyl)peroxydicarbonate Ester), dihexadecyl peroxydicarbonate, tert-butyl peroxybenzoate, tert-butyl peroxybenzoate, peroxyacetic acid, t-butyl peroxypivalate, tertiary deoxypivalate Hexyl ester, cumene peroxy neodecanoate, tert-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, isopropyl Benzene hydroperoxide, paraben hydrogen peroxide, di-tert-butyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide-alkane Base metal, oxy-alkyl metal, and the like.

The present invention provides a use of a thermosetting resin for producing a build-up plate, an adhesive for a copper foil, a semiconductor package, a flexible substrate, a cover film, an adhesive sheet, a sealant, a pure film, and a hard and soft film. Bonding plate, solder resist ink, high frequency flexible substrate, etc.

The present invention provides a use of a thermosetting resin composition for producing a laminate, a high-frequency substrate, a build-up plate, an adhesive for a copper foil, a prepreg, a semiconductor package, an IC carrier, and a vehicle board. Wait.

Example 1 (thermosetting resin P-1)

Dimerized fatty amine (1075/CRODA / amine price of 205) 54.7g (0.10mole), 5-(2,5-dioxotetrahydrofuran)-3-methyl-3-cyclohexene-1,2- Dicarbonic anhydride (B-4400/DIC) 25.08g (0.095mole), dimethylacetamide 10g, diisobutyl ketone 100g, triethylamine 0.01g, placed in a mechanical stirring, condensing tube, drying tube , the distillation receiver, nitrogen four-reaction reaction bottle, the reaction temperature is controlled at 20 ° C ~ 30 ° C, the reaction for 3 hours, heated to 130 ° C ~ 180 ° C azeotropic removal of water, reaction for 4 hours, remove the solvent under reduced pressure , the amine value was 7.4, the terminal amine polyimine was obtained, the temperature was lowered to 90 ° C, and 50 g of toluene and bis(3-ethyl-5-methyl-4-succinimide phenylene) were added. Methane 4.42g (0.010mole), reacted at 90 ° C for 10 hours, subjected to Michael addition reaction, and detected bis(3-ethyl-5-methyl-4-succinimide phenyl)methane residue 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)

86.0 g (0.100 mole) of pyrithione diamine (KF-8010/Shin-Etsu), 27.93 g (0.095 mole) of biphenyltetracarboxylic dianhydride, 10 g of dimethylacetamide, 100 g of diisobutyl ketone, and three 0.01g of amine, placed in a four-port reaction flask equipped with mechanical stirring, condensing tube, drying tube, distillation receiver, nitrogen, the reaction temperature is controlled at 20 ° C ~ 30 ° C, reaction for 2 hours, then heated to 130 ° C ~ 180 °C azeotropically remove water, react for 4 hours, remove the solvent under reduced pressure, and test the amine price to 5.4, to obtain the terminal amine polyimine, reduce the temperature to 90 ° C, add toluene 50g and two (3-B Base-5-methyl-4-succinimide phenyl)methane 4.42 g (0.010 mole), reacted at 90 ° C for 10 hours, subjected to Michael addition reaction, and detected by dichoethylene (2-ethyl-5) The residual amount of -methyl-4-succinimide phenyl)methane was 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-methyl 6-ethylaniline) 14.1 g (0.05 mole), bis(aminocyclohexyl)methane 10.5 g (0.05 mole), decane tetracarboxylic dianhydride (manufactured by DMS-Z21/Gelest) 66.5g (0.095mole), 10g of dimethylacetamide, 100g of diisobutyl ketone, 0.01g of triethylamine, placed in a mechanical stirring, condensing tube, drying tube, distillation In a four-neck reaction flask of nitrogen and nitrogen, the reaction temperature is controlled at 20 ° C to 30 ° C for 2 hours, then heated to 130 ° C to 180 ° C to azeotropically remove water, react for 4 hours, and remove the solvent under reduced pressure. Its amine price is 6.5, the terminal amine polyimine is obtained, the temperature is lowered to 90 ° C, 50 g of toluene and bis(3-ethyl-5-methyl-4-cis-butenylene phenyl)methane are added. 4.42g (0.010mole), reacted at 90 ° C for 10 hours, Michael addition reaction was carried out, and the residual amount of bis(3-ethyl-5-methyl-4-succinimide phenyl)methane was determined by GPC. 0.10%, the solvent was removed under reduced pressure to obtain a thermosetting resin P-3.

Example 4 (thermosetting resin P-4)

11.3 g (0.10 mole) of terephthalaldehyde, 114.2 g (0.20 mole) of diamine fatty amine (1075/CRODA / amine price), 50 g of xylene, placed in a mechanical stirring, condensing tube, drying tube In a four-neck reaction flask of distillation receiver and nitrogen gas, the reaction temperature is controlled at 80 ° C to 90 ° C for 12 hours, and the solvent is removed under reduced pressure to obtain an Azomethine-based diamine, and the amine price is determined. 90.5, join (PPHT/Japan Refined) 43.32g (0.095mole), dimethylacetamide 10g, diisobutyl ketone 100g, triethylamine 0.01g, the reaction temperature is controlled at 20 ° C ~ 30 ° C, the reaction for 2 hours, after Heat to 130 ° C ~ 180 ° C azeotropic removal of water, reaction for 4 hours, remove the solvent under reduced pressure, check the amine price of 1.8, to obtain the terminal amine polyimine, the temperature was reduced to 90 ° C, added toluene 50g And di(3-ethyl-5-methyl-4-cis-butenenimine phenyl)methane 4.42g (0.010mole), reacted at 90 ° C for 10 hours, subjected to Michael addition reaction, and detected by GPC two ( The residual amount of 3-ethyl-5-methyl-4-succinimide phenyl)methane was 0.06%, and the solvent was removed under reduced pressure to give a thermosetting resin P-4.

Example 5 (thermosetting resin P-5)

Putting terephthalic acid 13.4g (0.10mole), helium oxide diamine (KF-8010 / Shin-Etsu) 172.0g (0.200mole), xylene 50g, placed with mechanical stirring, condensation tube, drying tube, distillation In the four-neck reaction flask of the receiver and nitrogen, the reaction temperature was controlled at 80 ° C to 90 ° C for 12 hours, and the solvent was removed under reduced pressure to obtain an Azomethine-based diamine, and the amine value was determined to be 62.3. Add 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA-100/Nippon Chemical and Chemical Co., Ltd.) 28.5 g ( 0.095mole), dimethylacetamide 10g, diisobutyl ketone 100g, triethylamine 0.01g, the reaction temperature is controlled at 20 ° C ~ 30 ° C, the reaction is 2 hours, then heated to 130 ° C ~ 180 °C azeotropically remove water, react for 4 hours, remove the solvent under reduced pressure, and test the amine price to 3.9, to obtain the terminal amine polyimine, reduce the temperature to 90 ° C, add toluene 50g and two (3-B Base-5-methyl-4-succinimide phenyl)methane 4.42 g (0.010 mole), reacted at 90 ° C for 10 hours, subjected to Michael addition reaction, and detected by dichoethylene (2-ethyl-5) The residual amount of -methyl-4-cis-butenylene phenyl)methane was 0.06%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-5.

Example 6 (thermosetting resin P-6)

13.3 g (0.10 mole) of terephthalic acid, 28.2 g (0.10 mole) of 4,4'-methylenebis(2-methyl 6-ethylaniline), 21.0 g of bis(aminocyclohexyl)methane ( 0.10mole), 50g of xylene, placed in a four-reaction reaction flask equipped with mechanical stirring, condensing tube, drying tube, distillation receiver, nitrogen, the reaction temperature is controlled at 80 ° C ~ 90 ° C, reaction for 12 hours, decompression The solvent was removed to obtain an Azomethine-based diamine, and the amine value was 191. The oxirane tetracarboxylic dianhydride (manufactured by DMS-Z21/Gelest) was added to 66.5 g (0.095 mole) of dimethylacetonitrile. 10g of amine, 100g of diisobutyl ketone, 0.01g of triethylamine, the reaction temperature is controlled at 20 ° C ~ 30 ° C, reaction for 2 hours, then heated to 130 ° C ~ 180 ° C azeotropic removal of water, reaction for 4 hours, decompression The solvent was removed and the amine value was determined to be 4.7 to obtain the terminal amine polyimine. The temperature was lowered to 90 ° C, and 50 g of toluene and bis(3-ethyl-5-methyl-4-cis-butenylene) were added. Amine phenyl)methane 4.42g (0.010mole), reacted at 90 ° C for 10 hours, subjected to Michael addition reaction, G2 detection of bis(3-ethyl-5-methyl-4-succinimide phenylene phenyl The residual amount of methane is 0.07%, and the solvent is removed under reduced pressure to obtain a thermosetting Resin P-6.

Example 7 (thermosetting resin P-7)

11.3 g (0.10 mole) of terephthalic acid, 114.2 g (0.20 mole) of divalent fatty amine (1075/CRODA / amine price), 50 g of xylene, placed in a mechanical stirring, condensing tube, drying tube In the four-port reaction flask of distillation receiver and nitrogen gas, the reaction temperature is controlled at 80 ° C ~ 90 ° C, The solvent was removed under reduced pressure for 12 hours to give an Azomethine-based diamine, which was found to have an amine valence of 90.6, 50% of butanone and bis(3-ethyl-5-methyl-4-cis 88.4 g (0.20 mole) of eneltimine phenyl)methane, reacted at 90 ° C for 10 hours, subjected to Michael addition reaction, and detected by dichoethylene (2-ethyl-5-methyl-4-cis-butene) The residual amount of the amine phenyl)methane was 0.83%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P-7.

Example 8 (thermosetting resin P-8)

13.3 g (0.10 mole) of terephthalic acid, 86.0 g (0.100 mole) of oxirane diamine (KF-8010/Shin-Etsu), 21.0 g (0.10 mole) of bis(aminocyclohexyl)methane, 50 g of xylene , placed in a four-port reaction flask equipped with mechanical stirring, condensing tube, drying tube, distillation receiver, nitrogen, the reaction temperature is controlled at 80 ° C ~ 90 ° C, the reaction for 12 hours, the solvent is removed under reduced pressure to obtain a containing Azomethine-based diamine, the amine value was 96.1, 50% of butanone and 88.4 g of bis(3-ethyl-5-methyl-4-cis-butenylene phenyl)methane (0.20 mole) were added. The reaction was carried out at 90 ° C for 10 hours, and the Michael addition reaction was carried out to determine the residual amount of bis(3-ethyl-5-methyl-4-cis-buteneniminephenyl)methane as 0.86% by GPC. The solvent was removed to obtain a thermosetting resin P-8.

Example 9 (thermosetting resin P-9)

Dimerized fatty amine (1075/CRODA / amine price 205) 57.1g (0.10mole), added butanone 50g and bis(3-ethyl-5-methyl-4-synthene phenylimine phenyl) 88.4g (0.20mole) of methane was placed in a four-component reaction flask equipped with mechanical stirring, condenser, drying tube, distillation receiver and nitrogen. The reaction temperature was controlled at 80 ° C ~ 90 ° C, and reacted at 90 ° C for 10 hours. The Michael addition reaction was carried out, and the residual amount of bis(3-ethyl-5-methyl-4-cis-buteneniminephenyl)methane was determined by GPC to be 1.20%, and the solvent was removed under reduced pressure to obtain a thermosetting resin P. -9.

Example 10~18

Examples 10 to 18 are: 10 parts by weight of each of thermosetting resins P-1 to P9 and 10 parts by weight of toluene are stirred and dissolved to form a glue, and the glue is applied to a polyimide film having a thickness of 12.5 μm. The coating was dried to a thickness of 25 μm, and the coated polyimide film was dried at 50 ° C for 10 minutes and dried at 60 ° C for 30 minutes, thereby obtaining a cover film, adhering the cover film to a copper foil having a thickness of 35 μm, and hot pressing. 200 ° C / 40 Kg / 40 minutes, measuring its adhesion strength; coating the glue on the PET film, drying at 50 ° C for 10 minutes, drying at 60 ° C for 30 minutes at 150 ° C for 3 hours, and finally cured at 200 ° C 3 In the hour, a cured product having a film thickness of 0.2 mm was obtained, and the glass transition temperature, dielectric constant, dielectric loss, folding endurance, and adhesion strength were measured, and the data are shown in Table 1.

Comparative example 1

10 parts by weight of styrene-based polyphenylene ether (made by OPE-St-2200 / MGC ) and 10 parts by weight of toluene were stirred and dissolved into a glue solution, and the glue solution was applied to a polyimide film having a thickness of 12.5 μm and coated. The layer was dried to a thickness of 25 μm, and the coated polyimide film was dried at 50 ° C for 10 minutes and dried at 60 ° C for 30 minutes, thereby obtaining a cover film, and adhering the cover film to a copper foil having a thickness of 35 μm, and hot pressing 200. °C/40Kg/40min, the subsequent strength was measured; the glue was applied to the PET film, dried at 50 ° C for 10 minutes, dried at 60 ° C for 30 minutes, baked at 150 ° C for 3 hours, and finally cured at 200 ° C for 3 hours. A cured product having a film thickness of 0.2 mm was obtained, and the glass transition temperature, dielectric constant, dielectric loss, folding endurance, and adhesion strength were measured, and the data are shown in Table 1.

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

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

Dielectric loss (Df): Measured at a frequency of 1 GHz using a cavity made by Agilent.

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

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

○ indicates no crease

△ indicates crease

X indicates cracking

Example 19~27

Examples 19 to 27 are: 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. Liquid, the 2116 glass fiber cloth is impregnated with glue, and dried at 175 ° C for 2 ~ 15 minutes, thereby making a semi-cured prepreg, then laminating four prepregs, one 0.5 ounce copper on each of the upper and lower sides The foil is then subjected to hot pressing under the conditions of a temperature increase rate of 1 to 3 ° C /min to 230 ° C, and hot pressing at a temperature of 8 to 15 kg / cm 2 for 180 minutes, thereby obtaining a laminate and measuring the glass thereof. Transfer temperature, dielectric loss, dielectric constant, flame retardancy, tear strength, and flexural modulus are shown in Table 2.

Comparative example 2

10 parts by weight of styrene-based polyphenylene ether (made 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 are made into a glue, and 2116 The glass fiber cloth is impregnated with glue and dried at 175 ° C for 2 to 15 minutes to form a semi-cured prepreg, then four prepregs are laminated, one 0.5 ounce copper foil on each of the upper and lower sides, followed by Hot pressing, the condition is to increase the temperature to 230 ° C at 1 ~ 3 ° C / min, at this temperature with a pressure of 8 ~ 15 kg / cm ^ 2 for 180 minutes, thereby obtaining a laminate, measuring its glass transition temperature, Electrical loss, dielectric constant, flame retardancy, tear strength, and flexural modulus are shown in Table 2.

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

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

Dielectric loss (Df): After removing the copper foil from the laminate, it was measured at a frequency of 1 GHz using a cavity/network analyzer manufactured by Agilent.

Flame retardancy: After removing the copper foil from the laminate, it was measured by UL-94V vertical burning method.

Tear strength: The adhesion of the copper foil layer to the laminate, the force required to tear the copper foil vertically from the panel by 1/8 inch wide, in pounds per inch.

Bending elastic modulus: The Shimadzu AG-X universal testing machine was used in accordance with the method of JIS-K6911.

BMI-5000: bis(3-ethyl-5-methyl-4-cis-buteneniminephenyl)methane (manufactured by Designer Materials).

It can be seen from Table 1 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, a dielectric loss (Df) of 0.0034 or less, and a strength and a folding endurance ratio of conventional ethylene. The polyphenylene ether is more preferable, so 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; Table 2 shows the examples 19 to 27 of the present invention. The cured product of the thermosetting resin composition 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 superior to the comparative example. The cured product of the conventional vinyl polyphenylene ether composition has better tear strength and flexural modulus than the cured product of the vinyl polyphenylene ether composition of Comparative Example 2, so the present invention provides a thermosetting resin composition. It meets the requirements of low dielectric properties, flame retardancy, high tear strength and high flexural modulus of the next generation high frequency substrate and semiconductor package substrate.

The present invention provides a use of a thermosetting resin for producing a build-up plate, an adhesive for a copper foil, a semiconductor package, a flexible substrate, a cover film, an adhesive sheet, a sealant, a pure film, and a soft Hard bonding board, solder resist ink, high frequency flexible substrate, etc. The present invention provides a use of a thermosetting resin composition for producing a laminate, a high frequency substrate, and a buildup layer. An adhesive for a plate or a copper foil, a prepreg, a semiconductor component, an IC carrier, an in-vehicle plate, or the like.

The present invention has been described in connection with the foregoing specific embodiments and comparative examples, and those skilled in the art can make various changes based on the above description, and do not limit the scope of the patent application of the present invention.

Claims (4)

A thermosetting resin obtained by reacting a diamine compound with bismaleimide, characterized in that the molecule contains at least one chemical structure residue as shown in formula (I): Wherein R1 , R2 , R3 and R4 are the same or different and are represented by hydrogen, methyl or ethyl; the diamine compound is: H ₂ NA-NH ₂ ; A is selected from the group consisting of: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; X is selected from the group consisting of: , , C24~C48 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; B is selected from the group consisting of: One or more of the group consisting of; Y is selected from: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; Z is selected from the group consisting of: , And C16-C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; and p is selected from the group consisting of: An integer from 0 to 1000; q is selected from the group consisting of: 1 to 1000. A thermosetting resin composition comprising at least: (a) a compound containing two unsaturated groups, comprising: One or more of the group consisting of two N-substituted maleimine groups, and one or more of the groups; (b) a flame retardant comprising: (c) a thermosetting resin obtained by reacting a diamine compound with bismaleimide, characterized in that the molecule contains at least one chemical structure residue as shown in formula (I): Wherein R1 , R2 , R3 and R4 are the same or different and are represented by hydrogen, methyl or ethyl; the diamine compound is: H ₂ NA-NH ₂ ; A is selected from the group consisting of: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; X is selected from the group consisting of: , , C24~C48 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; B is selected from the group consisting of: One or more of the group consisting of; Y is selected from: C16~C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; Z is selected from the group consisting of: , And C16-C44 having a divalent hydrocarbon group of an aliphatic side chain, one or more of the group consisting of; n is an integer selected from: 1 to 1000; m is an integer selected from: 1 to 1000; and p is selected from the group consisting of: An integer from 0 to 1000; q is selected from the group consisting of: 1 to 1000. A use of a thermosetting resin as claimed in claim 1 for producing a build-up plate, an adhesive for a copper foil, a semiconductor package, a flexible substrate, a cover film, an adhesive sheet, a sealant, and a pure Film, soft and hard bonding board, solder mask ink, high frequency flexible substrate, etc. A use of a thermosetting resin composition as claimed in claim 2, which is used for producing a laminate, a high-frequency substrate, a build-up plate, an adhesive for a copper foil, a prepreg, a semiconductor package, and an IC carrier. Board, vehicle board, etc.