Biphenyl epoxy resin, resin composition and use thereof

Abstract

Disclosed in the present application are a biphenyl epoxy resin, a resin composition and the use thereof. The biphenyl epoxy resin comprises a compound shown as structural formula (1). The additional arrangement of a styrene substituent in the biphenyl epoxy resin, and the cooperation with a rigid biphenyl structure enable a cured product to have high heat resistance, low dielectric constant, low dielectric loss, high dimensional stability and high modulus.

Description

Biphenyl-type epoxy resin, resin composition and application thereof

[0001] The present application is based on and claims priority to Chinese patent application No. CN202410417968.8, filed on April 8, 2024, the entire contents of which are incorporated herein by reference. TECHNICAL FIELD

[0002] The present application belongs to the technical field of electronic materials, and relates to a biphenyl-type epoxy resin, and further relates to a resin composition and application of the resin composition in prepreg, laminated board, insulating board, insulating film, circuit board and electronic device. BACKGROUND

[0003] Epoxy resins are widely used in the field of electrical and electronic products due to their good moisture resistance, excellent mechanical properties and electrical properties.

[0004] With the progress of science and technology and the development of communication technology, electronic products are becoming smaller and smaller in size and more and more diversified in function, and the circuit design is also becoming more and more dense, so that more and more chips and modules need to be carried on the printed circuit board (PCB), which accordingly requires the epoxy resin used to have more excellent heat resistance, moisture resistance, dielectric properties and mechanical properties.

[0005] In existing epoxy resins, multi-aromatic ring structures such as naphthalene, anthracene and pyrene are introduced to obtain low water absorption and low thermal expansion. However, after introducing the multi-aromatic ring structure, the crosslinking density of the epoxy resin is reduced, resulting in poor heat resistance, toughness and dielectric properties, which cannot meet the higher requirements of electronic products. SUMMARY

[0006] In order to solve the problem that the existing epoxy resin cannot simultaneously meet the requirements of high heat resistance, low water absorption, low thermal expansion, excellent dielectric properties and high modulus, the present application provides a biphenyl-type epoxy resin, and a resin composition and a prepreg, laminated board, insulating board, insulating film, circuit board and electronic device prepared by using the resin composition.

[0007] To achieve one of the above application purposes, an embodiment of the present application provides a biphenyl-type epoxy resin comprising the following compound:

[0008] , structural formula (1),

[0009] wherein R is hydrogen or any one of C1-C5 alkyl, and n is an integer of 1-10.

[0010] As a further improvement of the embodiment of the present application, the biphenyl-type epoxy resin further comprises the following compound:

[0011] a compound represented by structural formula (2),

[0012] wherein n is an integer from 1 to 10.

[0013] As a further improvement of the embodiment of the present application, the weight percentage of the compound represented by structural formula (2) in the biphenyl type epoxy resin is 5-50%.

[0014] As a further improvement of the embodiment of the present application, in structural formula (1), R is hydrogen, methyl or tert-butyl.

[0015] As a further improvement of the embodiment of the present application, the preparation method of the biphenyl type epoxy resin comprises:

[0016] S1. 80-300 parts by weight of phenol and 0.5-6 parts by weight of a first catalyst are added to a reaction bottle, slowly stirred under nitrogen protection, 50-230 parts by weight of an aromatic mono-vinyl compound is added dropwise for 0.5-3 h, then kept for 30-180 min, the reaction temperature is 90-130℃, to obtain a substituted phenol;

[0017] S2. 50-200 parts by weight of the obtained substituted phenol is subjected to an electrophilic substitution reaction with 30-130 parts by weight of 4,4'-bis(chloromethyl) biphenyl or 4,4-dimethoxymethyl biphenyl in the presence of 0.01-3 parts by weight of a first catalyst, the reaction temperature is 110-150℃, and the reaction time is 1-3 h, to obtain a biphenyl type phenolic resin represented by structural formula (3);

[0018] a compound represented by structural formula (3),

[0019] wherein R is hydrogen or any one of C1-C5 alkyl, and n is an integer from 1 to 10;

[0020] S3. The obtained biphenyl type phenolic resin is subjected to an epoxidation reaction with epichlorohydrin, the reaction temperature is 50-120℃, and the reaction time is 0.5-3.5 h, to obtain a biphenyl type epoxy resin represented by structural formula (1).

[0021] As a further improvement of the embodiment of the present application, in S3, a biphenyl type phenolic resin represented by structural formula (4) is added, and subjected to an epoxidation reaction with epichlorohydrin, to obtain a mixture of the biphenyl type epoxy resin represented by structural formula (1) and the biphenyl type epoxy resin represented by structural formula (2);

[0022] a compound represented by structural formula (4),

[0023] wherein n is an integer from 1 to 10.

[0024] As a further improvement of the embodiment of the present application, in S3, the weight ratio of the biphenyl type phenol-formaldehyde resin represented by structural formula (4) to the biphenyl type phenol-formaldehyde resin represented by structural formula (3) is 5:95 to 50:50.

[0025] As a further improvement of the embodiment of the present application, in S1, the aromatic monovinyl compound is styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, 3-methylstyrene, 3-tert-butylstyrene, 3-ethylstyrene, 2-methylstyrene, 2-tert-butylstyrene or 2-ethylstyrene.

[0026] As a further improvement of the embodiment of the present application, the first catalyst is an acid catalyst.

[0027] As a further improvement of the embodiment of the present application, the first catalyst is benzene sulfonic acid or activated clay.

[0028] To achieve one of the above-mentioned purposes, the present application further provides a resin composition comprising, by weight of solid:

[0029] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0030] a curing agent, 1 to 60 parts by weight,

[0031] a second catalyst, 0.001 to 10 parts by weight;

[0032] wherein the first epoxy resin is the biphenyl type epoxy resin as described above;

[0033] the second epoxy resin is different from the first epoxy resin, and in the mixture of the first epoxy resin and the second epoxy resin, the weight ratio of the first epoxy resin to the second epoxy resin is 10:90 to 90:10.

[0034] As a further improvement of the embodiment of the present application, the second epoxy resin is at least one of dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate-modified epoxy resin, bisphenol A type epoxy resin, phenol type novolac epoxy resin, o-cresol novolac type epoxy resin, epoxidized polybutadiene resin, naphthalene ring-containing epoxy resin, bisphenol F type epoxy resin, trifunctional epoxy resin, hydrogenated bisphenol A epoxy resin or hydrogenated bisphenol F type epoxy resin.

[0035] As a preferred solution, the second epoxy resin is the naphthalene ring-containing epoxy resin.

[0036] As a further improvement of an embodiment of the present application, the curing agent is at least one of an amine curing agent, an active ester curing agent, an acid anhydride curing agent, and a phenol curing agent.

[0037] As an option, the amine curing agent is dicyandiamide, an aromatic diamine compound, or an aliphatic diamine compound.

[0038] As an option, the aromatic diamine compound is at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis(4-(4-aminophenoxy)phenyl)propane, bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthyl, diaminodiphenyl fluorene, and diaminanthraquinone.

[0039] As an option, the active ester curing agent includes at least one of the following structures in its structure:

[0040] , structure formula (5),

[0041] , structure formula (6),

[0042] , structure formula (7).

[0043] As a preferred option, the active ester curing agent is dicyclopentadienyl active ester or naphthyl active ester.

[0044] As a preferred option, the acid anhydride curing agent is styrene-maleic anhydride copolymer.

[0045] As a further improvement of an embodiment of the present application, the molar ratio of styrene to maleic anhydride in the styrene-maleic anhydride copolymer is 1:1, 2:1, 3:1, 4:1, 6:1, or 8:1, and the weight average molecular weight of the styrene-maleic anhydride copolymer is 1300-45000.

[0046] As an option, the phenol curing agent is phenol-formaldehyde resin or benzoxazine resin.

[0047] As a further improvement of an embodiment of the present application, the benzoxazine resin is ring-opened to form phenolic hydroxyl groups at high temperature.

[0048] As a further improvement of an embodiment of the present application, the resin composition includes, by weight of solids:

[0049] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0050] the active ester curing agent, 10 to 50 parts by weight,

[0051] the second catalyst, 0.001 to 10 parts by weight.

[0052] As a further improvement of an embodiment of the present application, the resin composition comprises, by weight of solids:

[0053] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0054] the phenol resin, 5 to 50 parts by weight,

[0055] the second catalyst, 0.001 to 10 parts by weight.

[0056] As a further improvement of an embodiment of the present application, the resin composition comprises, by weight of solids:

[0057] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0058] the styrene-maleic anhydride copolymer, 10 to 30 parts by weight,

[0059] the benzoxazine resin, 5 to 30 parts by weight;

[0060] the second catalyst, 0.001 to 10 parts by weight.

[0061] As an option, the second catalyst is at least one of an imidazole catalyst, a pyridine catalyst, an organophosphorus catalyst, and an organometallic salt catalyst.

[0062] As an option, the second catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 2-phenylimidazole, and zinc octoate.

[0063] As a further improvement of an embodiment of the present application, the resin composition further comprises, by weight of solids, 20 to 200 parts of an inorganic filler.

[0064] As an option, the inorganic filler is at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.

[0065] As a preferred solution, the inorganic filler is spherical silica.

[0066] As a further improvement of an embodiment of the present application, the inorganic filler is surface treated with a silane coupling agent, which is at least one of an amino silane coupling agent, an epoxy silane coupling agent or a carbon-carbon double bond-containing silane coupling agent.

[0067] As a further improvement of an embodiment of the present application, the resin composition further comprises 5 to 60 parts by weight of a flame retardant, based on the solid weight.

[0068] As an optional solution, the flame retardant is at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon flame retardant or an organic metal salt flame retardant.

[0069] As an optional solution, the bromine-based flame retardant is selected from decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or tetrabromophthalic acid amide.

[0070] As an optional solution, the phosphorus-based flame retardant is selected from inorganic phosphorus, condensed phosphoric acid ester compound, phosphoric acid compound, hypophosphorous acid compound, phosphorus oxide compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-HQ), 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphorus, (m is an integer from 1 to 5), phosphazene or modified phosphazene.

[0071] As an optional solution, the flame retardant is condensed phosphoric acid ester, hypophosphite or double DOPO compound.

[0072] The present application also provides the use of the above resin composition in prepreg, laminated board, insulating board, insulating film, circuit board and electronic device.

[0073] Thanks to the use of the above technical solution, the present application has the following beneficial effects compared with the prior art:

[0074] (1) By adding styrene substituent in the biphenyl type epoxy resin and combining with the rigid biphenyl structure, a cured product with high heat resistance, low dielectric constant, low dielectric loss, high dimensional stability and high modulus can be obtained.

[0075] (2) By using the aforementioned biphenyl type epoxy resin for the first epoxy resin and controlling the content thereof, the resin composition can have high heat resistance, low dielectric constant, low dielectric loss, high dimensional stability and high modulus, so as to be applicable to the field of high heat resistance high speed substrate materials; further by adding a certain content of the second epoxy resin, the content of the styrene substituent in the resin composition is controlled, so as to make the resin composition have higher modulus, and further effectively reduce the dielectric loss.

[0076] The terms "comprise" and variations of the term, such as "comprises" and "comprising," will be understood to imply a non-exclusive inclusion. Thus, these terms will be understood to allow for additional non-included features, components, steps, or steps. DETAILED DESCRIPTION

[0077] The technical solutions of the present application will be further described below in combination with specific embodiments. The following embodiments are only descriptive, not limiting, and cannot limit the protection scope of the present application. It should be understood that, unless otherwise specified and limited, the terms "first", "second", etc. are only for description purposes, and cannot be understood as indicating or implying relative importance.

[0078] The present application provides a biphenyl type epoxy resin, a resin composition, and a prepreg, a laminate, an insulating plate, an insulating film, a circuit substrate and an electronic device prepared by using the resin composition, i.e. the application of the resin composition in the prepreg, the laminate, the insulating plate, the insulating film, the circuit substrate and the electronic device.

[0079] Firstly, an embodiment of the present application provides a biphenyl type epoxy resin, comprising the following compound:

[0080] , structural formula (1),

[0081] Wherein, R is hydrogen or any one of C1-C5 alkyl, and n is an integer of 1-10.

[0082] By increasing the styrene substituent in the biphenyl type epoxy resin and combining with the rigid biphenyl structure, a cured product with high heat resistance, low dielectric constant, low dielectric loss, high dimensional stability and high modulus can be obtained.

[0083] Further, the biphenyl type epoxy resin further comprises the following compound:

[0084] , structural formula (2),

[0085] Wherein, n is an integer from 1 to 10.

[0086] By adding the compound shown in structural formula (2) into the biphenyl type epoxy resin, the dielectric loss and the thermal expansion coefficient can be further reduced while maintaining excellent heat resistance and high thermal decomposition temperature, achieving higher dimensional stability.

[0087] Further, in the biphenyl type epoxy resin, the weight percentage of the compound shown in structural formula (2) is 5-50%.

[0088] In this way, the content and proportion of styrene substituent in the biphenyl type epoxy resin can be controlled, so as to further effectively reduce the dielectric loss while maintaining a higher modulus value, improve the heat resistance and thermal decomposition temperature, and be suitable for high-heat-resistant high-speed substrate materials.

[0089] Preferably, in the structural formula (1), R is hydrogen, methyl or tert-butyl.

[0090] More preferably, in the structural formula (1), R is tert-butyl, so as to increase the carbon-hydrogen group in the biphenyl type epoxy resin, further reduce the dielectric loss value and the dielectric constant.

[0091] Further, the preparation method of the biphenyl type epoxy resin comprises:

[0092] S1. Add 80-300 parts by weight of phenol and 0.5-6 parts by weight of a first catalyst to a reaction bottle, slowly stir under nitrogen protection, and drop 50-230 parts by weight of an aromatic mono-vinyl compound for 0.5-3 h, then keep for 30-180 min, the reaction temperature is 90-130 ℃, to obtain a substituted phenol;

[0093] S2. Take 50-200 parts by weight of the obtained substituted phenol, and 30-130 parts by weight of 4,4'-bis(chloromethyl) biphenyl or 4,4-dimethoxymethyl biphenyl to undergo an electrophilic substitution reaction under 0.01-3 parts by weight of a first catalyst, the reaction temperature is 110-150 ℃, and the reaction time is 1-3 h, to generate a biphenyl type phenolic resin shown in structural formula (3);

[0094] , structural formula (3),

[0095] Wherein, R is hydrogen or any one of C1-C5 alkyl, and n is an integer from 1 to 10;

[0096] S3. The obtained biphenyl type phenolic resin is subjected to an epoxidation reaction with epichlorohydrin, the reaction temperature is 50-120 ℃, and the reaction time is 0.5-3.5 h, to obtain a biphenyl type epoxy resin shown in structural formula (1).

[0097] Further, in the present embodiment, in S3, a biphenyl type phenolic resin as shown in structural formula (4) is added and subjected to an epoxidation reaction with epichlorohydrin to obtain a mixture of the biphenyl type epoxy resin as shown in structural formula (1) and the biphenyl type epoxy resin as shown in structural formula (2).

[0098] , structural formula (4),

[0099] wherein n is an integer of 1 to 10.

[0100] Of course, in other embodiments, the mixture of the biphenyl type epoxy resin as shown in structural formula (1) and the biphenyl type epoxy resin as shown in structural formula (2) can also be obtained by directly adding the biphenyl type epoxy resin as shown in structural formula (2) to the biphenyl type epoxy resin as shown in structural formula (1).

[0101] Further, in S3, the weight ratio of the biphenyl type phenolic resin as shown in structural formula (4) to the biphenyl type phenolic resin as shown in structural formula (3) is 5:95 to 50:50, so that the weight ratio of the compound as shown in structural formula (2) in the mixture of the biphenyl type epoxy resin as shown in structural formula (1) and the biphenyl type epoxy resin as shown in structural formula (2) can be 5 to 50%.

[0102] Preferably, in S1, the aromatic mono-vinyl compound is styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, 3-methylstyrene, 3-tert-butylstyrene, 3-ethylstyrene, 2-methylstyrene, 2-tert-butylstyrene or 2-ethylstyrene.

[0103] Preferably, the first catalyst is an acidic catalyst. More preferably, the first catalyst is benzene sulfonic acid or activated clay.

[0104] An embodiment of the present application further provides a resin composition comprising, by weight of solids:

[0105] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0106] a curing agent, 1 to 60 parts by weight,

[0107] a second catalyst, 0.001 to 10 parts by weight;

[0108] wherein the first epoxy resin is the biphenyl type epoxy resin according to any one of claims 1 to 4.

[0109] The second epoxy resin is different from the first epoxy resin, and the weight ratio of the first epoxy resin to the second epoxy resin in the mixture of the first epoxy resin and the second epoxy resin is 10:90-90:10.

[0110] That is, the resin composition comprises, by weight of solids:

[0111] a first epoxy resin, 100 parts by weight,

[0112] a curing agent, 1-60 parts by weight,

[0113] a second catalyst, 0.001-10 parts by weight;

[0114] The first epoxy resin is a biphenyl type epoxy resin as described above.

[0115] Alternatively, the resin composition comprises, by weight of solids:

[0116] a mixture of a first epoxy resin and a second epoxy resin, 100 parts by weight,

[0117] a curing agent, 1-60 parts by weight,

[0118] a second catalyst, 0.001-10 parts by weight;

[0119] The first epoxy resin is a biphenyl type epoxy resin as described above, the second epoxy resin is different from the first epoxy resin, and the weight ratio of the first epoxy resin to the second epoxy resin in the mixture of the first epoxy resin and the second epoxy resin is 10:90-90:10.

[0120] By using the aforementioned biphenyl type epoxy resin as the first epoxy resin and controlling the content thereof, the resin composition can have high heat resistance, low dielectric constant, low dielectric loss, high dimensional stability and high modulus, and thus can be suitable for the field of high-heat-resistant high-speed substrate materials; further by adding a certain content of the second epoxy resin, the content of styrene substituent groups in the resin composition is controlled, the resin composition has higher modulus, and the dielectric loss is further effectively reduced.

[0121] Preferably, the second epoxy resin is at least one of a dicyclopentadiene epoxy resin, a phosphorus-containing epoxy resin, an isocyanate-modified epoxy resin, a bisphenol A type epoxy resin, a phenol type novolac epoxy resin, an o-cresol novolac type epoxy resin, an epoxidized polybutadiene resin, a naphthalene ring-containing epoxy resin, a bisphenol F type epoxy resin, a trifunctional epoxy resin, a hydrogenated bisphenol A epoxy resin, or a hydrogenated bisphenol F type epoxy resin. More preferably, the second epoxy resin is a naphthalene ring-containing epoxy resin.

[0122] Preferably, the curing agent is at least one of an amine curing agent, an active ester curing agent, an acid anhydride curing agent, and a phenol curing agent.

[0123] Preferably, the amine curing agent is dicyandiamide, an aromatic diamine compound, or an aliphatic diamine compound.

[0124] Preferably, the aromatic diamine compound is at least one of unsubstituted phenylenediamine, methylphenylenediamine, dimethylphenylenediamine, trimethylphenylenediamine, tetramethylphenylenediamine, xylene diamine, diaminopyridine, diaminodiphenylmethane, substituted diaminodiphenylmethane, bis(4-(4-aminophenoxy)phenyl)propane, bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, diaminobenzophenone, diaminodiphenyl ether, diaminodiphenyl sulfone, diaminobiphenyl, diaminodiphenyl sulfide, diaminobinaphthalene, diaminodiphenylfluorene, and diaminanthraquinone.

[0125] Preferably, the active ester curing agent comprises at least one of the following structures in its structure:

[0126] , structure formula (5),

[0127] , structure formula (6),

[0128] , structure formula (7).

[0129] More preferably, the active ester curing agent is dicyclopentadiene-based active ester or naphthyl active ester.

[0130] Specifically, the active ester is selected from HPC-8000, HPC-8000H, HPC-8000L, HPC-8150, HPC-8100, HPC-8100L, EXB-8500, HPC-8200, EXB-9451, EXB-9460, EXB-9460S, or EXB-9411, etc. prepared by DIC.

[0131] Preferably, the acid anhydride curing agent is a styrene-maleic anhydride copolymer.

[0132] Further, in the styrene-maleic anhydride copolymer, the molar ratio of styrene to maleic anhydride is 1:1, 2:1, 3:1, 4:1, 6:1, or 8:1, and the weight average molecular weight of the styrene-maleic anhydride copolymer is 1300-45000.

[0133] Preferably, the phenol curing agent is phenol-formaldehyde resin or benzoxazine resin.

[0134] More preferably, the benzoxazine resin ring-opens at high temperature to form phenolic hydroxyl groups.

[0135] As a preferred embodiment, the resin composition, by solid weight, comprises:

[0136] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0137] the active ester curing agent, 10 to 50 parts by weight,

[0138] the second catalyst, 0.001 to 10 parts by weight.

[0139] As another preferred embodiment, the resin composition, by solid weight, comprises:

[0140] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0141] the phenolic resin, 5 to 50 parts by weight,

[0142] the second catalyst, 0.001 to 10 parts by weight.

[0143] As still another preferred embodiment, the resin composition, by solid weight, comprises:

[0144] a mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight,

[0145] the styrene-maleic anhydride copolymer, 10 to 30 parts by weight,

[0146] the benzoxazine resin, 5 to 30 parts by weight;

[0147] the second catalyst, 0.001 to 10 parts by weight.

[0148] Preferably, the second catalyst is at least one of an imidazole catalyst, a pyridine catalyst, an organophosphorus catalyst, and an organometallic salt catalyst.

[0149] More preferably, the second catalyst is at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 2-phenylimidazole, and zinc octoate.

[0150] Further, the resin composition, by solid weight, further comprises 20 to 200 parts by weight of an inorganic filler.

[0151] The inorganic filler is preferably at least one of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, glass fiber powder.

[0152] More preferably, the inorganic filler is spherical silica.

[0153] Further, the inorganic filler is surface treated with a silane coupling agent, which is at least one of an amino silane coupling agent, an epoxy silane coupling agent, or a carbon-carbon double bond-containing silane coupling agent.

[0154] Further, the resin composition further comprises 5 to 60 parts by weight of a flame retardant, based on the solid weight.

[0155] The flame retardant is preferably at least one of a bromine-based flame retardant, a phosphorus-based flame retardant, a nitrogen-based flame retardant, an organic silicon flame retardant, an organic metal salt flame retardant.

[0156] The bromine-based flame retardant is preferably at least one of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene, or tetrabromophthalic acid amide.

[0157] The phosphorus-based flame retardant is preferably at least one of inorganic phosphorus, a condensed phosphoric acid ester compound, a phosphoric acid compound, a hypophosphorous acid compound, a phosphorus oxide compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris(2,6-dimethylphenyl)phosphane, (m is an integer of 1 to 5), , phosphazene, or modified phosphazene.

[0158] wherein the DOPO group is .

[0159] More preferably, the flame retardant is a condensed phosphoric acid ester, a hypophosphite, or a bis-DOPO compound.

[0160] The application also provides a prepreg comprising a reinforcing material and the aforementioned resin composition; the resin composition is wrapped on the reinforcing material.

[0161] The preparation method of the prepreg is as follows: dissolving the aforementioned resin composition with a solvent to prepare a glue solution, then coating the glue solution onto the reinforcing material by the method of immersion, taking out the immersed reinforcing material and baking at a temperature of 100 to 180°C for 1 to 15 min; after drying, the prepreg is obtained.

[0162] Optionally, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, and cyclohexane.

[0163] Optionally, the reinforcing material is selected from at least one of natural fibers, organic synthetic fibers, organic fabrics, and inorganic fabrics.

[0164] Preferably, the reinforcing material is a glass fiber cloth. The glass fiber cloth is preferably an open fiber cloth or a flat cloth. More preferably, the glass fiber cloth is an E-glass fiber cloth, an S-glass fiber cloth, or a Q-glass fiber cloth.

[0165] Furthermore, when the reinforcing material is a glass fiber cloth, the glass fiber cloth is chemically treated with a coupling agent. The coupling agent is preferably an epoxy silane coupling agent or an amino silane coupling agent.

[0166] The application also provides a laminate, which comprises a piece of the aforementioned prepreg and a metal foil arranged on at least one side surface of the prepreg, or which comprises a combined piece formed by stacking a plurality of pieces of the aforementioned prepreg on each other and a metal foil arranged on at least one side surface of the combined piece.

[0167] By using the technical solution, the laminate has low thermal expansion coefficient, high glass transition temperature, low dielectric constant, and low dielectric loss value.

[0168] The method for preparing the laminate is as follows: a metal foil is arranged on one side or both sides of a piece of the aforementioned prepreg, or at least two pieces of the prepreg are stacked to form a combined piece, a metal foil is arranged on one side or both sides of the combined piece, and the metal foil laminate is obtained by hot pressing. The pressing conditions of the hot pressing are as follows: the pressure is 0.2-2 MPa, the temperature is 150-250°C, and the pressing time is 2-4 h.

[0169] Preferably, the metal foil is selected from a copper foil or an aluminum foil. The thickness of the metal foil is 5 μm, 8 μm, 12 μm, 18 μm, 35 μm, or 70 μm.

[0170] The application also provides an insulating plate comprising the aforementioned resin composition.

[0171] The application also provides an insulating film comprising a carrier film and the aforementioned resin composition coated on the carrier film.

[0172] The insulating film is prepared by the following method: the aforementioned resin composition is dissolved with a solvent to form a glue solution, the glue solution is coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the insulating film.

[0173] Optionally, the solvent is selected from at least one of acetone, butanone, methyl isobutyl ketone, N,N-dimethylformamide, N,N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene, cyclohexane.

[0174] Optionally, the carrier film is selected from at least one of a PET film, a PP film, a PE film, a PVC film.

[0175] The present application also provides a circuit substrate comprising at least one of the aforementioned prepreg, laminated board, insulating board, and insulating film.

[0176] The present application also provides an electronic device comprising the aforementioned circuit substrate.

[0177] The technical solutions of the present application will be further described below in combination with some specific synthesis examples, embodiments, and comparative examples. Of course, these embodiments are only a part of the numerous changed embodiments of the present application, not all.

[0178] Synthesis Example 1

[0179] The present synthesis example discloses a preparation method of a biphenyl type epoxy resin, comprising the following steps:

[0180] S1. Add 95 g of phenol and 1 g of benzene sulfonic acid in a reaction bottle, slowly stir under nitrogen protection, and warm up to 105℃. After 1.5 h, drop 105 g of styrene, and then keep for 90 min to make the reaction complete, to obtain a phenol compound containing styrene substituent;

[0181] S2. Take 100 g of the phenol compound containing styrene substituent obtained in S1 and 70 g of 4,4'-bis(chloromethyl) biphenyl, and make an electrophilic substitution reaction under the catalysis of 0.5 g of benzene sulfonic acid, with a reaction temperature of 130℃ and a reaction time of 2 h, to generate a biphenyl type phenolic resin as shown in structural formula (3), and R in structural formula (3) is hydrogen;

[0182] S3. Make an epoxidation reaction of the biphenyl type phenolic resin obtained in S2 with epichlorohydrin, with a reaction temperature of 90℃ and a reaction time of 2 h, to obtain a biphenyl type epoxy resin A as shown in structural formula (1), and R in structural formula (1) is hydrogen.

[0183] Synthesis Example 2

[0184] The present synthesis example discloses a preparation method of a biphenyl type epoxy resin, comprising the following steps:

[0185] S1. Add 95 g of phenol and 1 g of benzene sulfonic acid in a reaction bottle, slowly stir under nitrogen protection, and heat to 105°C. After 1.5 h, add 120 g of 4-methylstyrene dropwise, and then keep for 90 min to complete the reaction to obtain a phenol compound containing a styrene substituent;

[0186] S2. Take 110 g of the phenol compound containing a styrene substituent obtained in S1 to react with 70 g of 4,4'-bis(chloromethyl) biphenyl under the catalysis of 0.5 g of benzene sulfonic acid to generate an electrophilic substitution reaction, the reaction temperature is 130°C, and the reaction time is 2 h to obtain a biphenyl type phenolic resin as shown in structural formula (3), and R in structural formula (3) is methyl;

[0187] S3. The biphenyl type phenolic resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin, the reaction temperature is 90°C, and the reaction time is 2 h to obtain a biphenyl type epoxy resin B as shown in structural formula (1), and R in structural formula (1) is methyl.

[0188] Synthesis Example 3

[0189] The synthesis example discloses a preparation method of a biphenyl type epoxy resin, including the following steps:

[0190] S1. Add 95 g of phenol and 1 g of benzene sulfonic acid in a reaction bottle, slowly stir under nitrogen protection, and heat to 105°C. After 1.5 h, add 120 g of 4-methylstyrene dropwise, and then keep for 90 min to complete the reaction to obtain a phenol compound containing a styrene substituent;

[0191] S2. Take 110 g of the phenol compound containing a styrene substituent obtained in S1 to react with 70 g of 4,4'-bis(chloromethyl) biphenyl under the catalysis of 0.5 g of benzene sulfonic acid to generate an electrophilic substitution reaction, the reaction temperature is 130°C, and the reaction time is 2 h to obtain a biphenyl type phenolic resin as shown in structural formula (3), and R in structural formula (3) is methyl;

[0192] S3. The biphenyl type phenolic resin obtained in S2 is subjected to an epoxidation reaction with epichlorohydrin, the reaction temperature is 90°C, and the reaction time is 2 h to obtain a biphenyl type epoxy resin B as shown in structural formula (1), and R in structural formula (1) is methyl.

[0193] Synthesis Example 4

[0194] The synthesis example discloses a preparation method of a biphenyl type epoxy resin, including the following steps:

[0195] S1. Add 95 g of phenol and 1 g of benzene sulfonic acid in a reaction bottle, slowly stir under nitrogen protection, and heat to 105°C. After 1.5 h, add 105 g of styrene dropwise, and then keep for 90 min to complete the reaction to obtain a phenol compound containing styrene substituent;

[0196] S2. Take 100 g of the phenol compound containing styrene substituent obtained in S1 and 70 g of 4,4'-bis(chloromethyl) biphenyl to undergo electrophilic substitution reaction under the catalysis of 0.5 g of benzene sulfonic acid, the reaction temperature is 130°C, and the reaction time is 2 h to generate a biphenyl type phenolic resin as shown in structural formula (3), and R in structural formula (3) is hydrogen;

[0197] S3. Take 70 g of the biphenyl type phenolic resin obtained in S2 and 30 g of a biphenyl type phenolic resin as shown in structural formula (4) to undergo epoxidation reaction with epichlorohydrin, the reaction temperature is 90°C, and the reaction time is 2 h to obtain a biphenyl type epoxy resin mixture D.

[0198] Each of Examples 1-6 and Comparative Examples 1-3 discloses a resin composition, the chemical components and contents of which are shown in Table 1, wherein the content of each chemical component is in parts by weight based on the solid weight.

[0199] Table 1

[0200]

[0201] Among them, the biphenyl type epoxy resin E is NC-3000 made by Japan Chemical, the naphthalene type epoxy resin is NC-7000 made by Japan Chemical, the phenolic resin is bisphenol A type phenolic resin made by Shengquan, the dicyclopentadienyl active ester is HPC-8000 made by DIC, the benzoxazine resin is bisphenol A type benzoxazine resin made by Dongcai, the styrene-maleic anhydride copolymer is EF40 made by Sartomer, the 2-methyl imidazole is made by Shikoku Chemical, the spherical silica is made by Lianrui with D50 of 3 μm, and the condensed phosphate is PX-200 made by Daiba.

[0202] Each of the above examples and comparative examples further discloses a prepreg, which comprises a glass fiber cloth as a reinforcing material and the resin composition coated on the glass fiber cloth by the method of impregnation. Among them, the glass fiber cloth is an open fiber cloth and is pretreated with an epoxy silane coupling agent in advance;

[0203] Among them, the prepreg is prepared by the following method:

[0204] The components of the above resin composition are dissolved in butanone respectively, stirred and mixed uniformly, and then diluted into a glue solution with a solid content of 65 wt%;

[0205] The E-glass fiber cloth as the reinforcing material is pretreated with an epoxy silane coupling agent, then dipped in the glue solution, taken out after impregnation, and placed in a blast drying oven at 160°C for 3-6 min to obtain a prepreg.

[0206] The above examples and comparative examples also respectively disclose a laminate prepared by the following method:

[0207] The above prepreg is cut to 300×300 mm, then one low-profile electrolytic copper foil with a thickness of 12 μm is placed on each side of the prepreg to form a stack, which is placed in a vacuum hot press and hot-pressed at a pressure of 1.5 MPa and a temperature of 220°C for 1.5 h to obtain a 1 mm thick copper-clad laminate.

[0208] The above examples and comparative examples also respectively disclose an insulating board comprising one of the above prepregs, which is prepared by a conventional preparation method of the prior art and thus will not be described here.

[0209] The above examples and comparative examples also respectively disclose a circuit substrate comprising one of the above prepregs, which is prepared by a conventional preparation method of the prior art and thus will not be described here.

[0210] The copper-clad laminates obtained in Examples 1-6 and Comparative Examples 1-3 are subjected to performance testing, and the test results are shown in Table 2. The performance testing methods include:

[0211] (1) Glass transition temperature (Tg): tested by DMA (thermal mechanical analysis) method according to the method specified in IPC-TM-650 2.4.25, with a temperature rising rate of 10°C / min and a frequency of 10 Hz.

[0212] (2) Dk (10 GHz): determined by the flat plate method in IPC-TM-650 2.5.5.9.

[0213] (3) Df (10 GHz): determined by the flat plate method in IPC-TM-650 2.5.5.9.

[0214] (4) X / Y axis thermal expansion coefficient (CTE): determined by TMA method according to IPC-TM-650 method, with a temperature rising rate of 5°C / min and a test temperature range of 50-120°C.

[0215] (5) Modulus: determined by TMA method in IPC-TM-650 2.4.24.4.

[0216] Table 1

[0217] Performance Tg / ℃ Dk Df CTE (X-Y, α1) / ℃-1 Modulus (GPa) Example 1 723.4 0.01 213 22 Example 2 683.3 6 0.01 142 3 Example 3 893.3 0.01 112 6 Example 4 783.4 6 0.01 312 5 Example 5 173.4 3 0.01 212 3 Example 6 743.4 6 0.01 312 4 Comparative Example 1 583.4 2 0.02 516 24 Comparative Example 2 623.5 8 0.01 615 23 Comparative Example 3 173.3 3 0.01 115 25

[0218] Referring to Table 2, compared with the comparative examples, the copper-clad laminated boards prepared from the resin compositions of the embodiments of the present application have high heat resistance, low dielectric constant, low dielectric loss, high dimensional stability and high modulus, and can be applied to the field of high-heat-resistant high-speed substrate materials.

[0219] It should be understood that although the present specification is described in terms of embodiments, not every embodiment contains only one independent technical solution, and the description of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

[0220] The above detailed description is only a specific description of the feasible embodiments of the present application, and is not intended to limit the protection scope of the present application, and any equivalent embodiments or changes made without departing from the spirit of the present application shall be included in the protection scope of the present application.

Claims

1. A biphenyl type epoxy resin, characterized in that, These compounds include: , structural formula (1), Wherein, R is hydrogen or any one of C1-C5 alkyl groups, and n is an integer of 1 to 10.

2. The biphenyl type epoxy resin according to claim 1, wherein Also included are the following compounds: , structural formula (2), Wherein, n is an integer from 1 to 10.

3. The biphenyl type epoxy resin according to claim 2, wherein The weight percentage of the compound represented by structural formula (2) is 5-50%.

4. The biphenyl type epoxy resin according to claim 1, characterized in that In the structural formula (1), R is hydrogen, methyl or tert-butyl.

5. The biphenyl type epoxy resin according to claim 1, characterized in that The preparation method thereof comprises: S1. Add 80 to 300 parts by weight of phenol and 0.5 to 6 parts by weight of the first catalyst to the reaction flask, slowly stir under nitrogen, add 50 to 230 parts by weight of an aromatic monoethylene compound dropwise over 0.5 to 3h, then maintain for 30 to 180min, the reaction temperature is 90 to 130 ° C to obtain a substituted phenol; S2. 50 to 200 parts by weight of the obtained substituted phenol is reacted with 30 to 130 parts by weight of 4,4'-bis(chloromethyl)biphenyl or 4,4-dimethoxymethylbiphenyl in the presence of 0.01 to 3 parts by weight of a first catalyst to undergo an electrophilic substitution reaction at a temperature of 110 to 150°C for 1 to 3 hours to produce a biphenyl-type phenolic resin as shown in structural formula (3); , structural formula (3), Wherein, R is hydrogen or any one of C1-C5 alkyl groups, and n is an integer from 1 to 10; S3. The obtained biphenyl phenolic resin is subjected to epoxidation reaction with epichlorohydrin at a reaction temperature of 50-120° C. and a reaction time of 0.5-3.5 h to obtain a biphenyl epoxy resin as shown in structural formula (1).

6. The biphenyl type epoxy resin according to claim 5, characterized in that In S1, the aromatic monovinyl compound is styrene, 4-methylstyrene, 4-tert-butylstyrene, 4-ethylstyrene, 3-methylstyrene, 3-tert-butylstyrene, 3-ethylstyrene, 2-methylstyrene, 2-tert-butylstyrene or 2-ethylstyrene.

7. The biphenyl type epoxy resin according to claim 5, characterized in that The first catalyst is an acidic catalyst.

8. A resin composition, characterized in that By solid weight, comprising: A mixture of the first epoxy resin and the second epoxy resin, or the first epoxy resin, 100 parts by weight, Curing agent, 1~60 parts by weight, The second catalyst, 0.001 to 10 parts by weight; Wherein, the first epoxy resin is the biphenyl type epoxy resin according to any one of claims 1 to 7; The second epoxy resin is different from the first epoxy resin. In the mixture of the first epoxy resin and the second epoxy resin, the weight ratio of the first epoxy resin to the second epoxy resin is 10:90 to 90:

10.

9. The resin composition according to claim 8, characterized in that The second epoxy resin is at least one of dicyclopentadiene epoxy resin, phosphorus-containing epoxy resin, isocyanate-modified epoxy resin, bisphenol A epoxy resin, phenol-type novolac epoxy resin, o-cresol-type epoxy resin, epoxidized polybutadiene resin, naphthalene ring-containing epoxy resin, bisphenol F epoxy resin, trifunctional epoxy resin, hydrogenated bisphenol A epoxy resin or hydrogenated bisphenol F epoxy.

10. The resin composition according to claim 8, characterized in that The curing agent is at least one of an amine curing agent, an active ester curing agent, an acid anhydride curing agent, and a phenol curing agent.

11. The resin composition according to claim 10, characterized in that The amine curing agent is dicyandiamide, an aromatic diamine compound or an aliphatic diamine compound.

12. The resin composition according to claim 10, characterized in that The structure of the active ester curing agent includes at least one of the following structures: , structural formula (5), , structural formula (6), , structural formula (7).

13. The resin composition according to claim 10, characterized in that The anhydride curing agent is styrene-maleic anhydride copolymer; The phenolic curing agent is phenolic resin or benzoxazine resin.

14. The resin composition according to claim 8, characterized in that The invention further comprises 20 to 200 parts by weight of an inorganic filler based on solid weight.

15. Use of the resin composition according to any one of claims 8 to 14 in prepregs, laminates, insulating boards, insulating films, circuit boards and electronic devices.

Images