JP2018016793A - Thermosetting resin, and composition and application of the same - Google Patents

Abstract

The present invention provides a thermosetting resin composition having properties such as a high glass transition temperature and low dielectric properties, and at the same time, further properties such as adhesiveness, elastic modulus and tear strength. A thermosetting resin obtained by reacting a diamine compound with bismaleimide. A thermosetting resin composition comprising at least (a) a compound containing two unsaturated groups, (b) a flame retardant, and (c) the thermosetting resin. A compound having two unsaturated groups is a compound having two P-vinylphenylenes or a compound having at least two N-substituted maleimide groups, and a compound having a diphenylphosphenyl as a flame retardant or a dibromophenyl ether oligomer A thermosetting resin composition, which is vinylbenzene. [Selection figure] None

Description

  The present invention relates to a thermosetting resin, a composition thereof, and an application. The composition includes at least (a) a compound containing two unsaturated groups, (b) a flame retardant, and (c) a thermosetting resin. Built-up plate, adhesive for copper foil, semiconductor packaging material, flexible substrate, coating film, bonding sheet, sealant, bonding sheet, rigid flexible substrate , Solder resist inks, high-frequency flexible substrates, high-frequency substrates, prepreg sheets, IC carrier boards, car-mounted boards, etc.

  With the advancement of communication electronics technology, signal transmission of high-speed traffic systems (ITS) of large computers, mobile communications, base stations, servers, routers and smart cars is developing towards higher frequencies and higher speeds. Of these, the low dielectric constant resin material is a key material in the high-speed transmission technology. The low dielectric constant (Dk) affects the signal transmission speed, and the low dielectric loss (Df) affects the signal transmission quality. The trend of mobile communication devices is toward higher speed and smaller size and lighter weight, high-density substrates are replacing conventional substrates, substrates are becoming thinner, multilayered, and densified, and semiconductors are becoming embedded. In addition, characteristics such as higher glass transition temperature and lower dielectric properties are required for the substrate material and the sealing material, and at the same time, further characteristics such as adhesion and elastic modulus are required, of which elastic modulus and expansion The coefficient affects the warpage and elastic modulus of the semiconductor sealing substrate, and directly affects the toughness of the substrate and the reliability of the holes.

  Patent document CN102993491A discloses a thermosetting resin composition, which improves the metal bond strength of phenolic polyphenylene ether with a butadiene polymer, and has a Df of 0.003 or more. , Dk is 3.2 or more.

  Patent document TW2015146181 discloses a resin composition containing (A) a polyimide resin, (B) a maleimide oligomer, (C) a thermosetting resin, and (D) a flame retardant. 007 or more and Dk is 2.9 or more.

    In known resin materials of the known art, only vinyl group polyphenylene ether (TWI250995) has relatively ideal dielectric properties (Dk of about 2.6, Df of about 0.003), and glass transition temperature of about 180 ° C. However, it is difficult to increase the glass transition temperature and the elastic modulus at the same time while the vinyl-based polyphenylene ether retains low dielectric properties, or the toughness, flex resistance and polyimide of the vinyl-based polyphenylene ether are difficult. There is still much room for improvement in the adhesion of film and copper foil.

The first problem to be solved by the present invention is a problem existing in the prior art. Polyphenylene ether and polytetrafluoroethylene have a low dielectric loss of Df (1 GHz) of 0.004 or less. Although industrial demands can be achieved, polyphenylene ether itself is very brittle, flex resistance and adhesive strength are not good, and polytetrafluoroethylene is difficult to process. Its characteristics are inadequate and cannot meet the demands and expectations of the industry. The second problem to be solved by the present invention is a problem existing in the prior art, and a polyphenylene ether resin and a cured product of a composition widely used for high-frequency substrates have a low dielectric loss (Df) and a low dielectric constant ( Dk), but its glass transition temperature is 180 ° C. or lower, and the substrate is becoming thinner, multi-layered, and higher in density, and the trend of technology toward the integration of semiconductors is not easy to dissipate heat. In order to solve this problem, it is essential to increase the glass transition temperature, and it is necessary to increase the tearing strength and flexural modulus at the same time as dealing with ultra-thinning. Can meet the requirements of packaging materials.

The technical means for solving the problems of the present invention is to provide a thermosetting resin obtained by reacting a diamine compound (diamine) with bismaleimide, characterized by at least one of the following formulas ( Including a chemical structure residue represented by 1):
Among them, R1, R2, R3 and R4 are the same or different and represent hydrogen, methyl, ethyl and propyl. Diamine compound is _{H 2 N-A-NH 2} .
A is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
X is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 24 to 48 carbon atoms.
B is
One or more selected from the group consisting of
Y is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
Z is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
n is an integer selected from 1 to 1000. m is an integer selected from 1 to 1000. p is an integer selected from 0 to 1000. q is an integer selected from 1 to 1000.

The present invention provides a thermosetting resin composition, and the composition includes at least the following:
A compound containing two unsaturated groups, including one or more selected from the group consisting of maleimide compounds having at least two N-substituted maleimide groups in one molecule;
Flame retardants, including
(C) A thermosetting resin obtained by reacting a diamine compound and bismaleimide, the feature of the thermosetting resin includes at least one chemical structure residue represented by the following formula (1) in the molecule:
Among them, R1, R2, R3 and R4 are the same or different and represent hydrogen, methyl, ethyl and propyl. Diamine compound is _{H 2 N-A-NH 2} .
A is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
X is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 24 to 48 carbon atoms.
B is
One or more selected from the group consisting of
Y is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
Z is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
n is an integer selected from 1 to 1000. m is an integer selected from 1 to 1000. p is an integer selected from 0 to 1000. q is an integer selected from 1 to 1000.

  The present invention provides applications for thermosetting resins, which include build-up layer boards, adhesives for copper foil, semiconductor packaging materials, flexible substrates, coating films, bonding sheets, sealing agents, bonding sheets. , Rigid flexible substrates, solder resist inks, high-frequency flexible substrates and the like are used.

  The present invention provides the use of a thermosetting resin composition, which is a laminated board, a high-frequency board, a buildup layer board, an adhesive for copper foil, a prepreg sheet, a semiconductor encapsulant, an IC carrier board, an on-vehicle mounting. Used in the manufacture of industrial boards.

  As an effect on the prior art, for example, vinyl group polyphenylene ether and polytetrafluoroethylene can achieve industrial requirements of low dielectric loss Df (1 GHz) 0.003 or less, but polyphenylene ether itself is very brittle. Also, the bending resistance and adhesive strength are not good, and polytetrafluoroethylene is difficult to process, so both of them have insufficient properties to be used for flexible substrates and meet the demands and expectations of the industry I can't. The present invention provides a thermosetting resin that has characteristics such as low dielectric properties and high adhesion and bending resistance at the same time, and can meet the demands of next-generation high-frequency flexible substrates. The second effect over the prior art is that the cured product of polyphenylene ether resin and composition widely used for high-frequency substrates has low dielectric loss (Df) and low dielectric constant (Dk), but its glass transition. The temperature is 180 ° C. or less, and the present invention has a flame retardant property, a low dielectric loss (Df), a low dielectric constant (Dk), a high glass transition, a tear strength and a bending elastic modulus, and is a next generation high frequency substrate and semiconductor. Provided are a composition that can meet the requirements of packaging materials and the like and the expectation of the industry, and a cured product thereof.

The thermosetting resin provided by the present invention is obtained by reacting a diamine compound and bismaleimide, and the characteristics thereof include at least one chemical structural residue represented by the following formula (1) in the molecule:
Among them, R1, R2, R3 and R4 are the same or different and represent hydrogen, methyl, ethyl and propyl. Diamine compound is _{H 2 N-A-NH 2} .
A is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
X is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 24 to 48 carbon atoms.
B is
One or more selected from the group consisting of
Y is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
Z is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
n is an integer selected from 1 to 1000. m is an integer selected from 1 to 1000. p is an integer selected from 0 to 1000. q is an integer selected from 1 to 1000.

The thermosetting resin provided by the present invention performs a Michael addition reaction (reaction one) between a diamine compound and bismaleimide at 50 ° C. to 180 ° C. to form a linear structure, and at the same time, doubles a small number of maleimide groups. There is also the possibility that the bond undergoes a side reaction (addition) with a secondary amine (reaction 2). When cured at 180 ° C. to 230 ° C., the double bond of the maleimide group is opened, and the radical of the maleimide group is homopolymerized. ) (Reaction 3), and the double bond of the maleimide group undergoes an addition reaction with the secondary amine (reaction 2) to form a cured product of a network bridge, and the reaction is as follows.

  The thermosetting resin provided by the present invention does not have high solubility in the solvent of bismaleimide and does not have good compatibility with the diamine compound, and cannot be used for curing after direct mixing. By passing through a prepolymerization reaction, it can be easily used because it can be dissolved in a solvent such as methyl ethyl ketone and toluene, and the bismaleimide in the cured product is a rigid chain and has a high glass transition temperature, low The diamine compound includes a flexible segment (soft segment) and a semi-flexible chain segment, and by adjusting the chain segment structure according to the ratio, an appropriate elastic modulus, dielectric constant, etc. The cured product has a network cross-linked structure, can reduce the expansion coefficient, and the diamine compound and The molecular structure of the copolymerization of sumerimide is very compatible with FCCSP and PoP encapsulating materials that have been thinned, and can also eliminate the risk of lowering adhesive strength after thinning the chip. Can be used for prepreg materials, coating materials, film materials, and the like.

  The thermosetting resin provided by the present invention is obtained by reacting a diamine compound with bismaleimide, and the bismaleimide is bis (maleimide phenyl) ether or bis (maleimidophenyl). ) Methane, bis (maleimidophenyl) sulfone, bis (maleimidophenyl) fluorene, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3-methyl-5-methyl-4-maleimidophenyl) methane Bis (3-ethyl-5-ethyl-4-maleimidophenyl) methane, m-phenylene bismaleimide, bis (maleimide) p-phenylene bismaleimide, bis (maleimide) o- Phenylene, bis (maleimide) toluene, bis (maleimide) biphenyl, bis (maleimide) methane, One selected from the group consisting of (maleimido) ethane, bis (maleimido) butane, bis (maleimido) hexane, bis (maleimido) heptane, bis (maleimido) octane, bis (maleimido) decane, and bis (maleimido) dodecane Or various kinds are included.

The thermosetting resin provided by the present invention is obtained by reacting a diamine compound and bismaleimide, and the diamine includes a terminal amino polyimide, an azomethine group-containing diamine, and a carbon number. A divalent hydrocarbon diamine having 16 to 44 aliphatic side chains, an aliphatic diamine having 16 to 44 carbon atoms, and an alicyclic-containing diamine having 16 to 44 carbon atoms, of which a fatty acid having 16 to 44 carbon atoms The divalent hydrocarbon diamine having a group side chain is obtained after reductive amination of a dimer containing an unsaturated fatty acid, and the number of carbons containing the unsaturated fatty acid is generally from 8 to 8 carbon atoms. Therefore, an amine dimer having 16 to 44 carbon atoms can be obtained after reductive amination of a dimer containing unsaturated fatty acid, and among them, an amine dimer having 36 carbon atoms is obtained. Including the following known structures:

The thermosetting resin provided by the present invention is obtained by reacting a diamine compound and bismaleimide, and the azomethine group-containing diamine in the diamine is terephthalaldehyde and a fatty acid having 16 to 44 carbon atoms. Divalent hydrocarbon diamine adducts having a group side chain, terephthalaldehyde and bis (aminocyclohexyl) methane adduct, terephthalaldehyde and 4,4'-methylenebis (2,6-dicyclohexylcyclohexylamine) adduct, terephthalaldehyde and 4,4′-methylenebis (2,6-diamylcyclohexylamine) adduct, terephthalaldehyde and 4,4′-methylenebis (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-dimethylcyclohexylamine) adduct, terephthalaldehyde and 4,4'- Methylene bis (2-methyl 6-ethylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylene bis (2-methyl 6-isopropylcyclohexylamine) adduct, terephthalaldehyde and 4,4'-methylene bis (2-methyl 6) -Butylcyclohexylamine) adduct, terephthalaldehyde and di (aminobenzene) methane adduct, terephthalaldehyde and 4,4'-methylenebis (2,6-dihexylaniline) (4,4'-methylenebis (2,6-dimethylaniline) )) Adduct, terephthalaldehyde and 4,4'-methylenebis (2,6-diamilaniline) Additives, terephthalaldehyde 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'-methylenebis (2,6-dimethylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis (2-methyl-6-ethylaniline) ) Adduct, terephthalaldehyde and 4,4'-methylenebis (2-methyl 6-isopropylaniline) adduct, terephthalaldehyde and 4,4'-methylenebis (2-methyl 6-butylaniline) adduct, terephthalaldehyde
One or more selected from the group consisting of azomethine group-containing diamines.

The thermosetting resin provided by the present invention is a dianhydride monomer used for the synthesis of a terminal amino group polyimide in the diamine.
One or more selected from the group consisting of The diamine monomers used in the synthesis of the terminal amino group polyimide in the diamine are bis (aminocyclohexyl) methane, 4,4′-methylenebis (2,6-dicyclohexylcyclohexylamine), 4,4′-methylenebis (2 , 6-Diamylcyclohexylamine), 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-methyl-6-butylcyclohexylamine), bis (aminobenzene) Methane, 4,4′-methylenebis (2,6-dihexylaniline), 4,4′-methylenebis (2,6-diamylaniline), 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-methyl 6-ethyl aniline), 4,4′-methylene bis (2-methyl 6-isopropyl aniline), 4,4′-methylene bis (2-methyl 6-butyl aniline), amine having 32 carbon atoms (amine) dimer), a carbon number 36 amine dimer, a carbon number 40 amine dimer, a carbon number 44 amine dimer, a carbon number 48 amine dimer, a divalent having an aliphatic side chain having 16 to 44 carbon atoms. One or more selected from the group consisting of hydrocarbons. Among them, the molar ratio of the diamine monomer and dianhydride monomer used for the synthesis of the terminal amino group polyimide in the diamine is 1 to 0.98 to 0.50.

  In the thermosetting resin of the present invention, the solvent used for the synthesis is benzene, toluene, xylene, mesitylene, 1,2,4-trimethylbenzene (1,2,4-trimethylbenzene)), Cyclohexane, 1-butanol, 2-butanol, isobutanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, tetrahydrofuran, methyl isoamyl ketone, cyclopentanone, cyclohexanone, dioxane, γ-butyrolactone, γ-valerolactone, γ-caprolactone , Β-butyrolactone, β-valerolactone, β-caprolactone, 3-methyloctanoyl-4-lactone, 4-hydroxy-3-pentenoic acid γ-lactone , Chloroform, dichloromethane, di A single or mixed solvent such as tylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, butyl acetate, diethylene glycol monobutyl ether acetate, methoxyethanol, ethoxyethanol, dimethylformamide, dimethylacetamide, etc. Including.

The present invention provides a thermosetting resin composition, and the composition includes at least the following:
A compound containing two unsaturated groups, including one or more selected from the group consisting of maleimide compounds having at least two N-substituted maleimide groups in one molecule;
Flame retardants, including
(C) A thermosetting resin obtained by reacting a diamine compound and bismaleimide, the feature of the thermosetting resin includes at least one chemical structure residue represented by the following formula (1) in the molecule:
Among them, R1, R2, R3 and R4 are the same or different and represent hydrogen, methyl, ethyl and propyl. Diamine compound is _{H 2 N-A-NH 2} .
A is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
X is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 24 to 48 carbon atoms.
B is
One or more selected from the group consisting of
Y is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
Z is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
n is an integer selected from 1 to 1000. m is an integer selected from 1 to 1000. p is an integer selected from 0 to 1000. q is an integer selected from 1 to 1000.

The present invention provides a thermosetting resin composition, and (a) the compound containing two unsaturated groups in the composition is:
One kind or many kinds selected from the group consisting of maleimide compounds having two N-substituted maleimide groups are included in one molecule even if they are not in a small molecule.

  The present invention provides a thermosetting resin composition, and (a) the compound containing two unsaturated groups in the composition has at least two N-substituted maleimide groups in one molecule. Maleimide compounds include bis (maleimidophenyl) ether, bis (maleimidophenyl) methane, bis (maleimidophenyl) sulfone, bis (maleimidophenyl) fluorene, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3-Methyl-5-methyl-4-maleimidophenyl) methane, bis (3-ethyl-5-ethyl-4-maleimidophenyl) methane, m-phenylenebismaleimide, bis (maleimido) p-phenylene, bis (maleimide) ) O-phenylene, bis (maleimido) toluene, bis (maleimido) biphenyl, bis (maleimido) methane, bis ( Reimide) ethane, bis (maleimido) butane, bis (maleimido) hexane, bis (maleimido) heptane, bis (maleimido) octane, bis (maleimido) decane, bis (maleimido) dodecane, phenylmethanemaleimide, 2 to 5 N -Including compounds having a substituted maleimide group.

The present invention provides a thermosetting resin composition, and the flame retardant (b) of the composition is:
Including one or more of the group consisting of

  The thermosetting resin composition provided by the present invention may further contain a curing accelerator, which includes azobisisobutyronitrile, azobis (2-isopropyl) butyronitrile, azobisisoheptanenitrile, benzoyl peroxide. ), Acetyl isobutyryl peroxide, diacetyl peroxide, peroxide (2,4-dichlorobenzoyl dichlorobenzoyl), peroxide (2-dimethyl benzylchlorobenzoyl), decanoyl peroxide, diisopropyl peroxid Oxydicarbonate, bis (3,5,5-trimethylhexanoyl) peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicyclohexyl propyl peroxy dicarbonate, dicyclohexyl peroxy dicarbonate ), Peroxydicarbonate bis (4-tert-butylcyclohexyl), peroxydicarbonate bis (2-ethylhexyl) ester (bis- (2-phenoxyethyl) peroxydicarbonate), peroxydicarbonate bis (2-phenoxyethyl) ester , Peroxydicarbonate bishexadecane ester, tert-butyl peroxybenzoate, tert-butyl peroxyphenylacetate, peracetic acid, tert-butyl peroxypivalate (tert -butyl peroxypivalate), tert-hexyl peroxypivalate, cumylperoxyneodecanoate, benzoyltert-butylperoxide, tert-butylhydroperoxide, butylperoxybenzoate ( butylperoxybenzoate), cumene hydroper Oxide, p-menthane hydroperoxide dicumyl peroxide, di-tert-butyl peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate, peroxide-alkyl metal, oxygen-alkyl metal, etc. including.

  The present invention provides applications for thermosetting resins, which include build-up layer boards, adhesives for copper foil, semiconductor packaging materials, flexible substrates, coating films, bonding sheets, sealing agents, bondings. Used in the manufacture of sheets, rigid flexible substrates, solder resist inks, high frequency flexible substrates and the like.

  The present invention provides the use of thermosetting resin, which includes laminated plates, high-frequency substrates, build-up layer plates, copper foil adhesives, prepreg sheets, semiconductor packaging materials, IC carrier boards, and vehicle mounting boards. Used in the manufacture of

Example 1 (thermosetting resin P-1)
Dimer fatty amine (1075 / manufactured by CRODA / amine number 205) 54.7 g (0.10 mole), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-Dicarboxylic anhydride (B-4400 / DIC) 25.08 g (0.095 mole), dimethylacetamide 10 g, diisobutyl ketone 100 g, triethylamine 0.01 g mechanically stirred, cooling tube, drying tube, distilled, The reaction temperature is controlled to 20 ° C. to 30 ° C., reacted for 3 hours, heated to 130 ° C. to 180 ° C. to remove water by azeotropic distillation, reacted for 4 hours, and reduced in pressure. When the amine value reached 7.4, the terminal amino group polyimide was obtained. The temperature was lowered to 90 ° C., and 50 g of toluene and bis (3-ethyl-5-methyl-4-mer were obtained. Reimidophenyl) methane (4.42 g, 0.010 mole) was added and reacted at 90 ° C. for 10 hours to perform a Michael addition reaction. Bis (3-ethyl-5-methyl-4-methyl) was detected by GPC detection. When the remaining amount of maleimidophenyl) methane is 0.15%, the solvent is removed under reduced pressure to obtain thermosetting resin P-1.

Example 2 (thermosetting resin P-2)
Siloxane diamine (KF-8010 / manufactured by Shin-Etsu) 86.0 g (0.100 mole), biphenyl tetracarboxylic dianhydride 27.93 g (0.095 mole), dimethylacetamide 10 g, diisobutyl ketone 100 g, triethylamine 0 .01 g was put into a mechanical stirring, cooling tube, drying tube, distillation receiver, and 4-necked reaction tube containing nitrogen, the reaction temperature was controlled at 20 ° C. to 30 ° C., reacted for 2 hours, and then heated to 130 ° C. to 180 ° C. Then, water was removed by azeotropic distillation, the reaction was carried out for 4 hours, the solvent was removed under reduced pressure, and when the amine value reached 5.4, a terminal amino group polyimide was obtained, the temperature was lowered to 90 ° C., and toluene 50 g And 4.42 g (0.010 mole) of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane were added. Then, the mixture was reacted at 90 ° C. for 10 hours, Michael addition reaction was performed, and when the remaining amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane was 0.22% by GPC detection, The solvent is removed by reducing the pressure to obtain a thermosetting resin P-2.

Example 3 (thermosetting resin P-3)
14.4 g (0.05 mole) of 4,4′-methylenebis (2-methyl-6-ethylaniline), 10.5 g (0.05 mole) of bis (aminocyclohexyl) methane, siloxane tetraacid dianhydride (DMS-Z21 / Gelest) 66.5 g (0.095 mole), 10 g of dimethylacetamide, 100 g of diisobutylketone, 0.01 g of triethylamine are mechanically stirred, cooling tube, drying tube, distillation receiver, put into a four-necked reaction tube containing nitrogen, and the reaction temperature is set. The temperature is controlled at 20 ° C. to 30 ° C. and reacted for 2 hours, then heated to 130 ° C. to 180 ° C. for azeotropic removal to remove moisture, reacted for 4 hours, the solvent is removed by decompression, and the amine value is 6 .5, a terminal amino group polyimide was obtained, the temperature was lowered to 90 ° C., 50 g of toluene and bis (3-ethyl-5-methyl-4-male Dophenyl) methane (4.42 g, 0.010 mole) was added, reacted at 90 ° C. for 10 hours, Michael addition reaction was performed, and bis (3-ethyl-5-methyl-4-maleimidophenyl was detected by GPC detection. ) When the remaining amount of methane becomes 0.10%, the solvent is removed by reducing the pressure to obtain thermosetting resin P-3.

Example 4 (thermosetting resin P-4)
13.4 g (0.10 mole) of terephthalaldehyde, 109.4 g (0.20 mole) of dimer fatty amine (1075 / manufactured by CRODA / amine number 205), 50 g of xylene, mechanically stirred, cooling tube, drying tube, distilled, The reaction temperature is controlled at 80 ° C. to 90 ° C., the reaction is performed for 12 hours, the solvent is removed by decompression, and an azomethine group-containing diamine is obtained. The amine value is 90.5. Once,
(PPHT / Nippon Seika Co., Ltd.) 43.32 g (0.095 mole), 10 g of dimethylacetamide, 100 g of diisobutylketone, 0.01 g of triethylamine are added and the reaction temperature is controlled at 20 ° C. to 30 ° C. for 2 hours. Then, the mixture was heated to 130 ° C. to 180 ° C. to remove water by azeotropic distillation, reacted for 4 hours, the solvent was removed under reduced pressure, and when the amine value reached 1.8, a terminal amino group polyimide was obtained, The temperature was lowered to 90 ° C., 50 g of toluene and 4.42 g (0.010 mole) of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane were added and reacted at 90 ° C. for 10 hours. ) Perform an addition reaction, and when the remaining amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is 0.06% by GPC detection, depressurize and remove the solvent. Except for thermosetting resin P-4.

Example 5 (thermosetting resin P-5)
13.4 g (0.10 mole) of terephthalaldehyde, 172.0 g (0.200 mole) of siloxane diamine (KF-8010 / manufactured by Shin-Etsu), and 50 g of xylene are mechanically stirred, a cooling tube, a drying tube, a distillation receiver, and 4 necks having nitrogen Put it in a reaction tube, control the reaction temperature to 80 ° C. to 90 ° C., let it react for 12 hours, remove the solvent under reduced pressure to obtain azomethine group-containing diamine, and when its amine value is 62.3, 4- (2,5-Dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA-100 / manufactured by Shin Nippon Rika) 28.5 g (0 0.095 mole), 10 g of dimethylacetamide, 100 g of diisobutylketone, and 0.01 g of triethylamine were added, and the reaction temperature was controlled at 20 to 30 ° C. React for 2 hours, then heat to 130 ° C to 180 ° C to remove water by azeotroping, react for 4 hours, remove the solvent under reduced pressure, and when the amine value becomes 3.9, the terminal amino group polyimide The temperature was lowered to 90 ° C., 50 g of toluene and 4.42 g (0.010 mole) of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane were added and reacted at 90 ° C. for 10 hours. When Michael addition reaction is performed and the remaining amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is 0.06% by GPC detection, the solvent is removed under reduced pressure and thermosetting is performed. Resin P-5 is obtained.

Example 6 (thermosetting resin P-6)
13.4 g (0.10 mole) of terephthalaldehyde, 28.2 g (0.10 mole) of 4,4′-methylenebis (2-methyl-6-ethylaniline), 21.0 g (0.10 mole) of bis (aminocyclohexyl) methane, 50 g of xylene was placed in a mechanical stirring, cooling tube, drying tube, distillation receiver, and 4-necked reaction tube containing nitrogen, the reaction temperature was controlled at 80 ° C. to 90 ° C., the reaction was performed for 12 hours, the solvent was removed by reduced pressure, and azomethine ( Azomethine) group-containing diamine was obtained, and when the amine value was 191, siloxane tetraacid dianhydride (manufactured by DMS-Z21 / Gelest) 66.5 g (0.095 mole), dimethylacetamide 10 g, diisobutyl ketone 100 g, triethylamine 0.01 g was added and the reaction temperature was controlled at 20 ° C. to 30 ° C. and reacted for 2 hours, After heating to 130 ° C. to 180 ° C. to remove water by azeotroping and reacting for 4 hours, the solvent was removed under reduced pressure, and when the amine value became 4.7, a terminal amino group polyimide was obtained, The temperature was lowered to 90 ° C., 50 g of toluene and 4.42 g (0.010 mole) of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane were added and reacted at 90 ° C. for 10 hours. ) When an addition reaction is performed and the remaining amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is 0.07% by GPC detection, the solvent is removed by reducing the pressure, and the thermosetting resin P- 6 is obtained.

Example 7 (thermosetting resin P-7)
13.4 g (0.10 mole) of terephthalaldehyde, 109.4 g (0.20 mole) of dimer fatty amine (1075 / manufactured by CRODA / amine number 205), 50 g of xylene, mechanically stirred, cooling tube, drying tube, distilled, The reaction temperature is controlled at 80 ° C. to 90 ° C., the reaction is carried out for 12 hours, the solvent is removed under reduced pressure to obtain an azomethine group-containing diamine, and the amine value is 90.6. Then, 50 g of butanone and 88.4 g (0.020 mole) of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane were added and reacted at 90 ° C. for 10 hours to perform Michael addition reaction. When the remaining amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is 0.83% by GPC detection, the solvent is removed by reducing the pressure to remove the thermosetting resin. Fat P-7 is obtained.

Example 8 (thermosetting resin P-8)
Mechanical stirring of 13.4 g (0.10 mole) of terephthalaldehyde, 186.0 g (0.100 mole) of siloxane diamine (KF-8010 / manufactured by Shin-Etsu), 21.0 g (0.10 mole) of bis (aminocyclohexyl) methane, and 50 g of xylene , Cooling tube, drying tube, distillation receiver, put into a 4-necked reaction tube with nitrogen, control the reaction temperature to 80-90 ° C., react for 12 hours, remove the solvent by decompression, azomethine (Azomethine) group-containing diamine When the amine value was 96.1, 50 g of butanone and 88.4 g (0.020 mole) of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane were added and added at 90 ° C. React for 10 hours, perform Michael addition reaction, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane by GPC detection When remaining battery capacity becomes 0.86% vacuo to remove solvent to give a thermosetting resin P-8.

Example 9 (thermosetting resin P-9)
Dimer fatty amine (1075 / manufactured by CRODA / amine number 205) 54.7 g (0.10 mole) butanone 50 g and bis (3-ethyl-5-methyl-4-maleimidophenyl) methane 88.4 g (0.020 mole) In addition, mechanical stirring, cooling tube, drying tube, distillation receiver, 4-necked reaction tube with nitrogen, reaction temperature is controlled at 80 ° C. to 90 ° C., reaction is performed at 90 ° C. for 10 hours, Michael When addition reaction is performed and the remaining amount of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane is 1.20% by GPC detection, the solvent is removed by reducing the pressure, and thermosetting resin P-9 Get.

Examples 10 to 18
Examples 10 to 18 are as follows in this order. 10 parts by weight of thermosetting resins P-1 to P-9 and 10 parts by weight of toluene were stirred and dissolved to form a gel solution, and the gel solution was applied onto a polyimide film having a thickness of 12.5 μm. The dry thickness was 25 μm, the applied polyimide film was dried at 50 ° C. for 10 minutes, dried at 60 ° C. for 30 minutes to obtain a coating film, and the coating film was adhered onto a 35 μm thick copper foil, Hot press is performed at 200 ° C./40 Kg for 40 minutes, and the adhesive strength is measured. The gel solution is applied onto a 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 to obtain a film thickness of 0.2 mm. The glass transition temperature, dielectric constant, dielectric loss, bending resistance, and adhesive strength of the cured product were measured, and the data are as shown in Table 1.

Comparative Example 1
Take 10 parts by weight of vinyl polyphenylene ether (OPE-St-2200 / MGC) and 10 parts by weight of toluene, stir and dissolve to form a gel solution, and apply the gel solution on a polyimide film having a thickness of 12.5 μm. The coating layer has a dry thickness of 25 μm, and the applied polyimide film is dried at 50 ° C. for 10 minutes and then dried at 60 ° C. for 30 minutes to obtain a coating film. The coating film is formed on a 35 μm thick copper foil. Adhesion is performed and hot pressing is performed at 200 ° C. and 40 kg for 40 minutes, and the adhesive strength is measured. The gel solution is applied onto a 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 to obtain a film thickness of 0.2 mm. The glass transition temperature, dielectric constant, dielectric loss, bending resistance, and adhesive strength of the cured product were measured, and the data are as shown in Table 1.

Glass transition temperature (Tg): Measured by TMA manufactured by TA.
Dielectric constant (Dk): Measured at 1 GHz with Agilent LCR Meter.
Dielectric loss: measured at 1 GHz using an Agilent cavity resonator.
Adhesive strength: The coating film is bonded onto a 35 μm thick copper foil, hot-pressed at 200 ° C. and 40 kg for 40 minutes, then cut into a sheet having a length of 10 cm and a width of 1 cm, and the copper foil layer is pulled upward in the vertical direction. The speed is 50 mm / min and the unit is N / cm.
Bending resistance: Visual inspection of the appearance of a cured product having a thickness of 0.2 mm after being folded in half at a 180 ° angle.
◯ indicates that there is no fold mark, Δ indicates that there is a fold mark, and X indicates that there is a crack.

Examples 19 to 27
Examples 19 to 27 are as follows in this order. 10 parts by weight 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 as a gel solution, and 2116 glass fiber cloth Impregnated with gel solution and dried at 175 ° C. for 2 to 15 minutes to produce semi-cured semi-cured sheet, then laminated 4 pieces of semi-cured sheet, each with 0.5 ounce copper on both top and bottom sides The foil is placed and then hot pressed, and the condition is that the temperature is increased to 1300C / min up to 230C, and hot pressing is performed at the temperature of 8-15KG / square centimeter for 180 minutes, The laminated plate was obtained by the following steps, and its glass transition temperature, dielectric loss, dielectric constant, interannuality, tear strength, and flexural modulus were measured, and the data are as shown in Table 2.

  10 parts by weight of vinyl polyphenylene ether (OPE-St-2200 / MGC), 10 parts by weight of a compound containing two unsaturated groups, 4 parts by weight of a flame retardant, 20 parts by weight of toluene as a gel solution, and 2116 glass fiber cloth Impregnated with gel solution and dried at 175 ° C. for 2 to 15 minutes to produce semi-cured semi-cured sheet, then laminated 4 pieces of semi-cured sheet, each with 0.5 ounce copper on both top and bottom sides The foil is placed and then hot pressed, and the condition is that the temperature is increased to 1300C / min up to 230C, and hot pressing is performed at the temperature of 8-15KG / square centimeter for 180 minutes, The laminated plate was obtained by the following steps, and its glass transition temperature, dielectric loss, dielectric constant, interannuality, tear strength, and flexural modulus were measured, and the data are as shown in Table 2.

Table 2

Glass transition temperature (Tg): Measured with TMA manufactured by TA after removing copper foil from the laminate.
Dielectric constant (Dk): After removing the copper foil from the laminate, the dielectric constant (Dk) was measured at 1 GHz using an Agilent LCR Meter.
Dielectric loss: After removing copper foil from the laminate, measured at 1 GHz with Agilent cavity resonator / network analyzer.
Flame retardancy: measured by UL-94V vertical combustion test after removing copper foil from laminate.
Tear strength: Adhesive strength of the copper foil layer to the laminate, the amount of force required to peel a 1/8 inch wide copper foil vertically from the plate surface, in pounds / inch.
Flexural modulus: Shimadzu AG-X universal testing machine is used according to JIS-K6911.

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

  From Table 1, the thermosetting resins P-1 to P-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 thermosetting resin provided by the present invention is low dielectric property, high adhesiveness and flex resistance of the next generation high-frequency flexible substrate, because it can be seen that the adhesive strength and flex resistance are more preferable than the conventional vinyl polyphenylene ether. Meet the requirements of From Table 2, the cured products of the thermosetting resin compositions of Examples 19 to 27 of the present invention have a flame retardancy of V-0 class, a glass transition temperature of 190 to 254 ° C., and a dielectric loss (Df). 0.0032 or less, dielectric constant (Dk) is 2.4 or less, which is superior to the cured product of the conventional vinyl polyphenylene ether composition of Comparative Example 2, and the expressions relating to tear strength and flexural modulus are also vinyl Polyphenylene of Comparative Example 2. Since the thermosetting resin composition provided by the present invention is found to be superior to the cured product of the ether composition, the low dielectric property, flame retardancy, and high tear strength of the next-generation high-frequency substrate and semiconductor sealing substrate Meets the demand for high flexural modulus.

  Applications of the thermosetting resin provided by the present invention include build-up layer boards, adhesives for copper foil, semiconductor packaging materials, flexible substrates, coating films, bonding sheets, sealing agents, bonding sheets, rigid flexible substrates. Used in the manufacture of solder resist inks, high-frequency flexible substrates and the like. Applications of the thermosetting resin composition provided by the present invention include the production of laminates, high-frequency substrates, build-up layer plates, copper foil adhesives, prepreg sheets, semiconductor packaging agents, IC carrier boards, vehicle mounting boards, etc. Used for.

  The present invention has been described according to the specific examples and comparative examples described above, and those skilled in the art can make various changes based on the above description. The scope of patent applications is not limited.

Claims (4)

A thermosetting resin obtained by reacting a diamine compound and bismaleimide and containing at least one chemical structure residue represented by the following formula (1) in the molecule.
(R1, R2, R3, and R4 are the same or different and represent hydrogen, methyl, ethyl, and propyl. The diamine compound is H ₂ N—A—NH ₂ .
A is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
X is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 24 to 48 carbon atoms.
B is
One or more selected from the group consisting of
Y is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
Z is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
n is an integer selected from 1 to 1000. m is an integer selected from 1 to 1000. p is an integer selected from 0 to 1000. q is an integer selected from 1 to 1000. ) At least the following (a) a compound containing two unsaturated groups, (b) a flame retardant, (c) a thermosetting resin composition containing a thermosetting resin,
A compound containing two unsaturated groups, including one or more selected from the group consisting of maleimide compounds having at least two N-substituted maleimide groups in one molecule;
A flame retardant comprising one or more of the group consisting of:
(C) A thermosetting resin obtained by reacting a diamine compound and bismaleimide, and the feature of the thermosetting resin includes at least one chemical structure residue represented by the following formula (1) in the molecule.
(R1, R2, R3, and R4 are the same or different and represent hydrogen, methyl, ethyl, and propyl. The diamine compound is H ₂ N—A—NH ₂ .
A is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
X is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 24 to 48 carbon atoms.
B is
One or more selected from the group consisting of
Y is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
Z is
One or more selected from the group consisting of divalent hydrocarbons having an aliphatic side chain having 16 to 44 carbon atoms.
n is an integer selected from 1 to 1000. m is an integer selected from 1 to 1000. p is an integer selected from 0 to 1000. q is an integer selected from 1 to 1000. )   Used for manufacturing build-up layer boards, adhesives for copper foil, semiconductor packaging materials, flexible substrates, coating films, bonding sheets, sealants, bonding sheets, rigid flexible substrates, solder resist inks, high-frequency flexible substrates, etc. The use of the thermosetting resin according to claim 1.   The thermosetting resin composition according to claim 2, which is used for production of a laminated board, a high-frequency board, a build-up layer board, an adhesive for copper foil, a prepreg sheet, a semiconductor packaging agent, an IC carrier board, a board for mounting on a car and the like. Uses.