CN114106267B - Thermosetting resin composition containing styrene compound and preparation method and application thereof - Google Patents

Thermosetting resin composition containing styrene compound and preparation method and application thereof Download PDF

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CN114106267B
CN114106267B CN202111442676.2A CN202111442676A CN114106267B CN 114106267 B CN114106267 B CN 114106267B CN 202111442676 A CN202111442676 A CN 202111442676A CN 114106267 B CN114106267 B CN 114106267B
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resin composition
parts
styrene compound
thermosetting resin
divinyl
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CN114106267A (en
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李兵兵
包欣洋
席奎东
粟俊华
殷小龙
谭拱峰
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Nanya New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

The invention relates to a thermosetting resin composition containing a styrene compound, which comprises the following raw material components in parts by weight: 15-50 parts of unsaturated triblock copolymer, 35-75 parts of polyfunctional styrene compound, 5-25 parts of auxiliary cross-linking agent and 0.2-3 parts of free radical polymerization initiator; the unsaturated triblock copolymer is of the ase:Sub>A-B-ase:Sub>A type block structure wherein the ase:Sub>A block is ase:Sub>A poly (alkenyl arene) polymer comprising mono alkenyl arene units and the B block is ase:Sub>A non-hydrogenated poly (acyclic conjugated diene) polymer comprising polymerized units of at least one acyclic conjugated diene. The resin composition of the invention not only has low dielectric constant and low dielectric loss, but also has small change rate of dielectric loss after moisture absorption, low water absorption, high thermal stability and good reliability, and the cured product of the thermosetting resin composition has dielectric loss factor below 0.0014 at 10GHz and can be used for manufacturing multilayer printed circuit boards with excellent processability, low dielectric property and high reliability.

Description

Thermosetting resin composition containing styrene compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of resin compositions, in particular to a thermosetting resin composition containing a styrene compound, and a preparation method and application thereof.
Background
With the rapid development of electronic technology, high-frequency signal transmission is required for high-capacity computer systems and electronic products such as communication base stations, servers, storage devices and the like. However, the transmission loss of the electric signal is greater as the transmission frequency of the signal is higher, and the transmission reliability of the signal is lowered due to the decrease of the transmission signal loss, and therefore, the dielectric loss factor of the substrate must be further lowered at a high frequency and a high transmission rate. The low dielectric resin material is a key material for the high frequency and high transmission device nowadays, so as to meet the future use requirement of high speed information transmission.
Currently, the printed circuit board uses polyphenylene oxide resin (PPO, or referred to as polyphenylene oxide resin) to lower the dielectric constant Dk and dielectric loss factor Df of the substrate, and is used in middle-high-end copper-clad plates and printed wiring boards due to its low dielectric loss and good heat resistance, environmental reliability, but dielectric loss appears to be insufficient at higher frequencies. Therefore, further development of a resin composition having a lower dielectric dissipation factor Df is required as an active development target in the current industry.
Disclosure of Invention
The invention aims to solve the problems and provide a thermosetting resin composition containing a styrene compound, a preparation method and application thereof.
The thermosetting resin composition has low dielectric constant and low dielectric loss, and has the advantages of small change rate of dielectric loss after moisture absorption, low water absorption, high thermal stability and good reliability. In addition, the thermosetting resin composition prevents occurrence of macroscopic phase separation of the resin system, and achieves excellent processability, low dielectric properties, and high heat resistance.
The aim of the invention can be achieved by the following technical scheme:
A thermosetting resin composition comprising a styrene compound, the composition comprising the following components: the cured product of the thermosetting resin composition has a dielectric dissipation factor at 10GHz of 0.0014 or less, and comprises an unsaturated triblock copolymer (a), a polyfunctional styrene compound (b), a co-crosslinking agent (c) and a radical polymerization initiator (d).
Further, the composition comprises the following components in parts by mass: 15-50 parts of unsaturated triblock copolymer (a), 35-75 parts of polyfunctional styrene compound (b), 5-25 parts of auxiliary cross-linking agent (c) and 0.2-3 parts of free radical polymerization initiator (d).
The unsaturated triblock copolymer has a number average molecular weight Mn of 5,000-50,000g/mol as measured by gel permeation chromatography GPC, has narrow molecular weight control, and a ratio PDI of weight average molecular weight Mw to number average molecular weight Mn of less than or equal to 1.20, wherein the poly (alkenyl arene) structural unit accounts for 30-75% of the total mass of the triblock copolymer.
The unsaturated triblock copolymer is of an A-B-A type block structure, wherein the A block is ase:Sub>A poly (alkenyl arene) polymer comprising at least high Tg mono alkenyl arene units having ase:Sub>A Tg >100 ℃ or >125 ℃, wherein the A block GPC peak molecular weight Mp is less than 3,5000g/mol of poly (alkenyl arene) homopolymers, examples include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, alphase:Sub>A-methylstyrene, p-alphase:Sub>A-dimethylstyrene, vinyl-benzocyclobutene, vinyl biphenyl, adamantylstyrene, 1-diphenyl-ethylene, and benzofullerenes;
Wherein the B block is a non-hydrogenated poly (acyclic conjugated diene) polymer comprising polymerized units of at least one acyclic conjugated diene; the polymer has a high-reactivity structural unit, and a side group has an unsaturated double bond structure; GPC peak molecular weight Mp of B block is greater than 3,000g/mol and less than 3,0000g/mol. Wherein the poly (acyclic conjugated diene) polymer is obtained by anionic polymerization and has highly selective 1, 2-vinyl structural units, wherein the molar ratio of the 1, 2-vinyl polyolefin structure to the whole B block is more than 85%, and the ratio of the 1, 2-vinyl polyolefin structure is more than 90%. The non-hydrogenated poly (acyclic conjugated diene) polymer structure may be exemplified by 1, 2-polybutadiene or 1, 2-polyisoprene.
The molecular structure of the polyfunctional styrene compound (B) is shown in the following formula (1),
Wherein R represents a hydrocarbon skeleton, R 1 represents a C1-C20 hydrocarbon group, R 2,R3,R4 represents a hydrogen atom or a C1-C6 hydrocarbon group, R 2,R3,R4 may be the same or different, m is an integer of 1 to 4, and n is an integer of 2 or more.
The polyfunctional styrene compound has a number average molecular weight of 1000g/mol or less, preferably a molecular weight of 170g/mol or more and 800g/mol or less. In the present invention, the small molecule vinyl compound may be exemplified by, but not limited to, any one or more of the following chemical structures of p, p '-divinyl-1, 2-diphenylethane (p, p' -BVPE), m '-divinyl-1, 2-diphenylethane (m, m' -BVPE), m, p '-divinyl-1, 2-diphenylethane (m, p' -BVPE), p '-divinyl-1, 2-diphenylmethane (p, p' -BVPM), m '-divinyl-1, 2-diphenylmethane (m, m' -BVPM), m, p '-divinyl-1, 2-diphenylmethane (m, p' -BVPM), and isomers of p, p '-divinyl-1, 2-diphenylpropane (p, p' -BVPP), m '-divinyl-1, 2-diphenylpropane (m, m' -BVPP), m, p '-divinyl-1, 2-diphenylpropane (m, p' -BVPP). Wherein, p, p 'represents para-position of benzene ring, m, m' represents meta-position of benzene ring. Further, the polyfunctional styrene compound is preferably p, p '-divinyl-1, 2-diphenylethane (p, p' -BVPE).
The auxiliary cross-linking agent (c) comprises one or more of styrene, divinylbenzene, triallyl isocyanurate, an acrylic ester compound, a methacrylic ester compound or maleimide resin.
Further, the auxiliary crosslinking agent contains an unsaturated double bond structure, can form a curable crosslinking structure with the unsaturated triblock copolymer, the polyfunctional styrene compound and the like, improves the mechanical strength and the glass transition temperature of the material, improves the bonding strength of the resin and the copper foil, and improves the flowability of the resin.
The radical polymerization initiator (d) includes a first radical initiator d1 having a half-life temperature of 80 to 120 ℃ in one hour and a second radical initiator d2 having a half-life temperature of 130 to 170 ℃ in one hour. The mass fraction of the resin composition is 0.2-3 parts by mass of the total mass of the radical polymerization initiators.
The first and second free radical initiators may each initiate a crosslinking reaction of unsaturated double bonds in the resin composition at different temperatures (i.e., at a temperature above the first and second crosslinking temperatures, respectively). Thus, the resin composition is partially crosslinked at about a first crosslinking temperature (i.e., a relatively low temperature of 80-120 ℃) and is further crosslinked at about a second crosslinking temperature (i.e., a relatively high temperature of 130-170 ℃). Thus, the first free radical initiator may be characterized as a relatively low temperature free radical initiator. In contrast, the second free radical initiator may be characterized as a relatively high temperature free radical initiator.
The resin composition performs partial crosslinking reaction at a lower temperature of 80-120 ℃ to form a prepreg, still has good reactivity and fluidity, and the prepreg formed by the first crosslinking temperature has good stability without excessive reaction to cause adverse problems in hot press curing production because the partially reacted unsaturated double bonds need to be further cured at a temperature higher than the second crosslinking temperature, namely 130-170 ℃ to form a substrate material.
The first radical initiator and the second radical initiator may each be an organic peroxide or an azo compound, the first radical initiator and the second radical initiator being different from each other. Preferably, the first radical initiator may be dibenzoyl peroxide or 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane and the second radical initiator may be di-t-butyl peroxide, cumyl hydroperoxide, t-butyl hydroperoxide, or 3,5, 7-pentamethyl-1, 2, 4-trioxepane.
Further, the composition further comprises a flame retardant (e) and an inorganic filler (f); the specific content is as follows: 10-40 parts of flame retardant (e) and 50-100 parts of inorganic filler (f).
The flame retardant comprises one or more of decabromodiphenyl ethane, decabromodiphenyl ether, octabromodiphenyl ether, ethylene bis-tetrabromophthalimide and tris (tribromophenyl) isocyanurate.
The inorganic filler is a low-dielectric synthetic spherical silica filler, the filler is spherical silica filler with the surface treated by vinyl or allyl or (methyl) acrylic ester silane coupling agent, and the dielectric loss of the spherical silica filler is less than 0.0014 at the frequency of 10 GHz; the average particle diameter D50 of the flame retardant and the inorganic filler is selected to be 0.5-5 mu m.
The production method of the prepreg comprises the following steps: soaking a fabric into the thermosetting resin composition, and then heating and drying the fabric at a first crosslinking temperature of 80-120 ℃ after soaking the fabric in the low-dielectric electronic-grade glass fiber cloth to obtain a prepreg; the low-dielectric electronic-grade glass fiber cloth is formed by alternately weaving warp yarns and weft yarns, wherein the warp yarns and the weft yarns are all composed of monofilaments, the whole electronic-grade glass fiber cloth structure is in a flattened form, and the warp yarns and the weft yarns are all fiber wires with low dielectric constants.
A metal foil-clad laminate produced by superposing a conductive foil on the prepreg; the average surface roughness of the conductive foil is smaller than 1.5 mu m, and the surface of the conductive foil is treated by a silane coupling agent.
The multilayer printed circuit board is manufactured by matching the prepreg and the metal foil-clad laminated board, wherein the loss factor Df of the multilayer printed circuit board at 10GHz is less than or equal to 0.0014, and the dielectric constant Dk at 10GHz is less than 3.3.
Compared with the prior art, the invention has the following advantages:
(1) The invention uses novel polymer containing unsaturated triblock, the designed molecular structure has good compatibility of resin system, and the middle block is of regular 1, 2-olefin block structure, thus not only having good reactivity, but also having low dielectric property;
(2) The polyfunctional styrene compound has a regular rigid skeleton structure, and the cured product of the polyfunctional styrene compound has extremely low dielectric loss tangent value in terms of dielectric loss, thereby being beneficial to achieving the purpose of the low dielectric loss thermosetting resin composition; meanwhile, the rigid structure of the glass has high glass transition temperature and ultrahigh heat resistance, and the heat stability and reliability of the cured base material can be improved.
(3) By controlling the polymerization reaction of the resin composition, the crosslinking reaction of the unsaturated double bonds in the resin composition can be initiated by controlling the high and low temperature radical initiator, i.e. the first radical initiator and the second radical initiator at different temperatures (above the first crosslinking temperature and the second crosslinking temperature, respectively).
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
According to one aspect of the present invention, there is provided a thermosetting resin composition containing a styrene compound, comprising the following components in parts by mass: 15-50 parts of unsaturated triblock copolymer (a), 35-75 parts of polyfunctional styrene compound (b), 5-25 parts of auxiliary crosslinking agent (c) and 0.2-1 part of free radical polymerization initiator (d); 10-40 parts of flame retardant (e) and 50-100 parts of inorganic filler (f).
Wherein the unsaturated triblock copolymer has a number average molecular weight Mn of 5,000-50,000g/mol as determined by gel permeation chromatography GPC, has narrow molecular weight control, and a ratio PDI of weight average molecular weight Mw to number average molecular weight Mn of less than or equal to 1.20, wherein the poly (alkenyl arene) structural units account for 30-75% of the total mass thereof.
The unsaturated triblock copolymer is of the ase:Sub>A-B-ase:Sub>A type block structure, the ase:Sub>A block being ase:Sub>A poly (alkenyl arene) polymer comprising mono alkenyl arene units, and the B block being ase:Sub>A non-hydrogenated poly (acyclic conjugated diene) polymer comprising polymerized units of at least one acyclic conjugated diene. The a block is a poly (alkenyl arene) polymer comprising at least high Tg mono alkenyl arene units having a Tg >100 ℃ or >125 ℃, wherein the a block is a poly (alkenyl arene) homopolymer having a GPC peak molecular weight Mp of less than 35,000 g/mol; the B block has high reactivity structural units, the side group has an unsaturated double bond structure, the poly (acyclic conjugated diene) polymer is obtained through anionic polymerization, and the poly (acyclic conjugated diene) polymer has highly selective 1, 2-vinyl structural units, wherein the 1, 2-vinyl polyolefin structure accounts for more than 85% of the mole ratio of the whole B block, and the GPC peak molecular weight Mp of the B block is more than 3,000g/mol and less than 30,000g/mol. For example, the a block comprises one or more of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α -methylstyrene, p- α -dimethylstyrene, vinyl-benzocyclobutene, vinylbiphenyl, adamantylstyrene, 1-diphenyl-ethylene, or benzofullerenes; the B block comprises one or both of 1, 2-polybutadiene or 1, 2-polyisoprene.
The molecular structure of the polyfunctional styrene compound (b) is represented by the following formula (1):
Wherein R represents a hydrocarbon skeleton, R 1 represents a C1-C20 hydrocarbon group, R 2,R3,R4 represents a hydrogen atom or a C1-C6 hydrocarbon group, R 2,R3,R4 may be the same or different, m is an integer of 1 to 4, n is an integer of 2 or more, and the number average molecular weight of the polyfunctional styrene compound (b) is a vinyl compound having a number average molecular weight of 1000g/mol or less.
For example, vinyl compounds include, but are not limited to, any one or more of p, p ' -divinyl-1, 2-diphenylethane, m, m ' -divinyl-1, 2-diphenylethane, m, p ' -divinyl-1, 2-diphenylethane, p, p ' -divinyl-1, 2-diphenylmethane, m, m ' -divinyl-1, 2-diphenylmethane, m, p ' -divinyl-1, 2-diphenylmethane and p, p ' -divinyl-1, 2-diphenylpropane, m, m ' -divinyl-1, 2-diphenylpropane, m, p ' -divinyl-1, 2-diphenylpropane, wherein p, p ' represents the para-position of the benzene ring and m, m ' represents the meta-position of the benzene ring.
For example, the co-crosslinking agent (c) includes one or more of styrene, divinylbenzene, triallyl isocyanurate, acrylate compounds, methacrylate compounds, or maleimide resins;
The radical polymerization initiator (d) comprises a first radical initiator (d 1) having a half-life temperature of 80 to 120 ℃ for one hour and a second radical initiator (d 2) having a half-life temperature of 130 to 170 ℃ for one hour, the mass fraction of the resin composition being 0.2 to 1 part by mass based on the total mass of the radical polymerization initiators; the first radical initiator and the second radical initiator are each an organic peroxide or an azo compound. For example, the first radical initiator may be dibenzoyl peroxide or 1, 1-bis (t-butylperoxy) -3, 5-trimethylcyclohexane and the second radical initiator may be di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxide, or 3,5, 7-pentamethyl-1, 2, 4-trioxepane.
The thermosetting composition also comprises a flame retardant (e) and an inorganic filler (f), wherein the specific content is as follows: 10-40 parts of flame retardant (e) and 50-100 parts of inorganic filler (f); for example, the flame retardant includes one or more of decabromodiphenylethane, decabromodiphenylether, octabromodiphenylether, ethylene bis-tetrabromophthalimide, tris (tribromophenyl) isocyanurate; the inorganic filler is a low-dielectric synthetic spherical silica filler, the filler is a spherical silica filler with the surface treated by vinyl or allyl or (methyl) acrylic ester silane coupling agent, and the dielectric loss of the spherical silica filler is less than 0.0014 at the frequency of 10 GHz; the average particle diameter D50 of the flame retardant and the inorganic filler is selected in the range of 0.5 to 5. Mu.m.
The preparation method of the thermosetting resin composition comprises the steps of firstly dissolving an unsaturated triblock copolymer (a) and a polyfunctional styrene compound (b) in a solvent, then adding a crosslinking aid (c), uniformly mixing and stirring, then adding a free radical polymerization initiator (d), and obtaining the thermosetting resin composition containing the styrene compound after dispersion treatment, wherein a flame retardant and/or an inorganic filler can be added between the free radical polymerization initiator (d).
The prepared thermosetting resin composition is used for manufacturing prepregs, metal foil-clad laminates and multilayer printed circuit boards.
When the prepreg is manufactured, the fabric is immersed into a thermosetting resin composition, and then the prepreg is obtained after the fabric is immersed in low-dielectric electronic-grade glass fiber cloth and then heated and dried; the low-dielectric electronic-grade glass fiber cloth is formed by alternately weaving warp yarns and weft yarns, wherein the warp yarns and the weft yarns are all composed of monofilaments, the whole electronic-grade glass fiber cloth structure is in a flattened form, and the warp yarns and the weft yarns adopt fiber wires with low dielectric constants.
Manufacturing a metal foil-clad laminate, wherein the laminate is prepared by overlapping a conductive foil with a prepreg; the average surface roughness of the conductive foil is less than 1.5 mu m, and the surface of the conductive foil is treated by a silane coupling agent.
And manufacturing a multi-layer printed circuit board, wherein the multi-layer printed circuit board is manufactured by matching a prepreg and a metal foil clad laminated board, the loss factor Df of the multi-layer printed circuit board at 10GHz is less than or equal to 0.0014, and the dielectric constant Dk at 10GHz is less than 3.3.
The following are specific examples of examples 1 to 5 and comparative examples 1 to 3
Examples 1 to 3
The prepreg solutions of the thermosetting resin compositions were prepared according to the formulations listed in table 1: the unsaturated triblock polymer SBS-A (Mn 26,000g/mol, PDI=1.18, st/Bd/St=25/50/25,1,2-vinyl content 92%, nippon Caddse:Sup>A Co., td.) and the polyfunctional styrene compound BVPE (p, p' -divinyl-1, 2-diphenylethane, seisakusho technology Co., td.) were dissolved in toluene solvent, then se:Sup>A co-crosslinking agent TAIC (triallyl isocyanurate, nippon chemical Co., td.) was added, mixed and stirred uniformly, then se:Sup>A flame retardant SAYTEX8010 (decabromodiphenyl ethane, D50 particle size 3.5um, americse:Sup>A Yabao chemical Co., td.) and an inorganic filler SE00XX (spherical silicse:Sup>A filler, D50 particle size 2.5um, sci Co., td.) were added, respectively, after being uniformly dispersed by se:Sup>A high-speed rotary mixer, se:Sup>A low-temperature radical polymerization initiator BPO (dibenzoyl peroxide, azkyamse:Sup>A chemical Co., half-life temperature was 95 ℃ C.) and se:Sup>A high-temperature radical polymerization initiator DCP (dicumyl peroxide, azkyse:Sup>A chemical Co., td.) were added, and se:Sup>A heat curing agent was added, and se:Sup>A pre-dip resin was mixed, and se:Sup>A thermoplastic resin composition was obtained after mixing was obtained.
Immersing a glass fiber fabric (1078L 2 low dielectric glass fiber cloth manufactured by AST company) in the prepreg of the thermosetting resin composition, drying at 120 ℃ for 5min, and removing toluene solvent to obtain a prepreg; then, the prepreg was laminated with 6 sheets, and the upper and lower surfaces thereof were sandwiched with Hoz HVLP copper foils (Rz-0.8 um, sanjing copper foil Co., ltd.), and then heat-pressed and cured at 190℃for 120min from room temperature at a heating rate of 2℃per minute under a pressurizing pressure of 4MPa to prepare a metal-clad laminate.
Examples 4 to 5
The prepreg solutions of the thermosetting resin compositions were prepared according to the formulations listed in table 1: the unsaturated triblock polymer SBS-B (Mn 8,440g/mol, PDI=1.07, st/Bd/St=15/70/15, 1, 2-vinyl content 94%, nippon Cao Dai Co., ltd.) and the polyfunctional styrene compound BVPE (p, p' -divinyl-1, 2-diphenylethane, changzhou Seisakusho technology Co., ltd.) were dissolved in toluene solvent, then a co-crosslinking agent TAIC (triallyl isocyanurate, nippon Kagaku Co., ltd.) was added, mixed and stirred uniformly, then a flame retardant SAYTEX8010 (decabromodiphenyl ethane, D50 particle size 3.5um, america Bao chemical Co., ltd.) and an inorganic filler SE00XX (spherical silica filler, D50 particle size 2.5um, nylon process silicon material Co., ltd.) were added, and after being uniformly dispersed by a high-speed rotation mixer, a low-temperature radical polymerization initiator BPO (dibenzoyl peroxide, one-hour half-life temperature was 95 ℃ C.) and a high-temperature radical polymerization initiator TAIC (DCP chemical Co., ltd.) were added, and the half-life time was 137 m epoxy resin was mixed, and stirred uniformly, respectively, and the thermosetting resin composition was obtained.
Immersing a glass fiber fabric (1078L 2 low dielectric glass fiber cloth manufactured by AST company) in the prepreg of the thermosetting resin composition, drying at 120 ℃ for 4min, and removing toluene solvent to obtain a prepreg; then, the prepreg was laminated with 6 sheets, and the upper and lower surfaces thereof were sandwiched with Hoz HVLP copper foils (Rz-0.8 um, sanjing copper foil Co., ltd.), and then heat-pressed and cured at 190℃for 90min from room temperature at a heating rate of 2.5℃per minute under a pressurizing pressure of 3.5MPa to prepare a metal-clad laminate.
Comparative example 1
The prepreg of the thermosetting resin composition of comparative example 1 was prepared by uniformly mixing and stirring unsaturated polybutadiene B2000 (mn 2,100g/mol, pdi= 1.17,1,2 —vinyl content 88%, japan soida corporation) and polyfunctional styrene compound BVPE (p, p' -divinyl-1, 2-diphenylethane, a company of hedyotis science and technology) in toluene solvent, then adding auxiliary crosslinking agent TAIC (triallyl isocyanurate, japan chemical company, a company of japan), further adding flame retardant saptex 8010 (decabromodiphenylethane, D50 particle size 3.5um, american elegance chemical company, b.m.), inorganic filler SE00XX (spherical silica filler, D50 particle size 2.5um, silicon materials, b.m.), uniformly dispersing by a high-speed rotary mixer, and then adding low-temperature radical polymerization initiator BPO (dibenzoyl peroxide, a half-life temperature of 95 ℃ C., a company of the family of the chemical industry, b.a. of the one hour half-life of the chemical industry, b.a. of the family of the peroxide, and a company of the high-temperature radical polymerization initiator DCP (a company of the family of the chemical industry, b.a small half-life of the temperature of the chemical industry, a, b.a small ℃ of the family of the price, b.a.of the chemical industry, b.a, b.of the heat-stable resin) and stirring the thermosetting resin composition.
Immersing a glass fiber fabric (1078L 2 low dielectric glass fiber cloth manufactured by AST company) in the prepreg of the thermosetting resin composition, drying at 120 ℃ for 5min, and removing toluene solvent to obtain a prepreg; then, 6 prepregs are overlapped, the upper surface and the lower surface are clamped by Hoz HVLP copper foils (Rz-0.8 um, sanjing copper foils Co., ltd.) and then are subjected to hot press curing molding at 190 ℃/120min under the pressurizing pressure of 4MPa at the temperature rising rate of 2 ℃/min from the room temperature to prepare the copper-clad plate.
Comparative example 2
In comparative example 2, only unsaturated triblock polymer SBS-A was used as se:Sup>A main resin, se:Sup>A polyfunctional styrene compound BVPE was not used, then se:Sup>A auxiliary cross-linking agent TAIC (triallyl isocyanurate, japanese chemical Co., td.) was added, mixed and stirred uniformly, then se:Sup>A flame retardant SAYTEX8010 (decabromodiphenyl ethane, D50 particle size 3.5um, americse:Sup>A chemical Co., td.) and an inorganic filler SE00XX (spherical silicse:Sup>A filler, D50 particle size 2.5um, jinzhi Si Co., td.) were added, and after uniform dispersion by se:Sup>A high-speed rotary mixer, se:Sup>A low-temperature radical polymerization initiator BPO (dibenzoyl peroxide, half-life temperature per hour was 95 ℃ C., aromax chemical Co., td.) and se:Sup>A high-temperature radical polymerization initiator DCP (dicumyl peroxide, half-life temperature per hour was 137 ℃ C., aromax chemical Co., td.) were added, and mixed and stirred, respectively, se:Sup>A prepreg containing se:Sup>A thermosetting resin composition was obtained; and then preparing the copper-clad plate by the same method.
Comparative example 3
Adjusting on the basis of the embodiment 2, adding a free radical polymerization initiator into a high-temperature initiator DCP, mixing and stirring to obtain a prepreg containing a thermosetting resin composition, immersing a glass fiber fabric (1078L 2 low-dielectric glass fiber cloth manufactured by AST company) into the prepreg of the thermosetting resin composition, drying at 120 ℃ for 5min, and removing toluene solvent to obtain a prepreg; then, 6 prepregs are overlapped, the upper surface and the lower surface are clamped by Hoz HVLP copper foils (Rz-0.8 um, sanjing copper foils Co., ltd.) and then are subjected to hot press curing molding at 190 ℃/120min under the pressurizing pressure of 4MPa at the temperature rising rate of 2 ℃/min from the room temperature to prepare the copper-clad plate.
Table 1 specific raw material formulations of examples 1 to 5 and comparative examples 1 to 3
The performance test was performed on the prepared copper clad laminate, the test method is as follows, and the test results are shown in table 2.
Glass transition temperature (Tg): the measurement was performed using a DMA instrument test according to the DMA test method specified in IPC-TM-650.2.4.24.4.
Coefficient of Thermal Expansion (CTE) in the Z-axis: the measurement was performed by using TMA instrument and according to the TMA test method defined in IPC-TM-650.2.4.24.
Copper foil Peel Strength (PS): the test was performed using an Shimadzu tensile machine according to the test method prescribed by IPC-TM-650.2.4.8.
Dielectric constant (Dk) and dielectric dissipation factor (Df): dielectric constant and dielectric loss factor test methods were as defined in IPC-TM-650.2.5.5.9.
Autoclave cooking experiment (PCT): the laminates were subjected to a retort test at 120℃and measured according to the test method prescribed by IPC-TM-650.2.6.16.
288 ℃ Layering time (T288): the test was performed using TMA equipment and was performed according to the test method specified in IPC-TM-650.2.4.24.1.
Flame retardancy: the test classification was carried out according to the method of flammability of materials specified in UL-94.
Heat resistance: refers to the property that a substance can still maintain its excellent physical and mechanical properties under the heated condition.
Resin system compatibility: taking the cross section of the base material, observing microscopic uniformity of the cured resin under SEM, and if the phenomenon of resin agglomeration occurs, obtaining the incompatible resin.
Table 2 test results for examples 1 to 5 and comparative examples 1 to 3
As can be seen from Table 2, the copper clad laminates prepared in examples 1 to 5 were excellent in appearance, the loss factor Df at 10GHz was less than or equal to 0.0018, and the dielectric constant Dk at 10GHz was less than 3.3; meanwhile, the laminated board has good thermal property, and the DMA glass transition temperature is more than or equal to 225 ℃; the copper-clad plate has a lower thermal expansion coefficient, a CTE of less than 2.35 percent and good heat resistance T288 which can be more than 60 minutes, and the copper-clad plate is immersed in tin for 10 seconds for three times. In addition, from SEM testing of the cut sheet of the laminate, it was found that the unsaturated triblock copolymer, the polyfunctional styrene compound and the auxiliary crosslinking agent did not undergo phase separation or the like after completion of curing.
From the data of comparative example 1 and example 5, comparative example 1 did not employ an unsaturated triblock polymer, but rather polybutadiene, it was seen that both the dielectric constant Dk and the loss tangent Df of polybutadiene resin were inferior to those of the unsaturated triblock polymer; the polybutadiene can cause low peel strength of the copper foil, the delamination time is only 32 minutes at 288 ℃, and the copper-clad plate is exploded after tin immersion, which indicates that the heat resistance is poor; in addition, polybutadiene resins have poor compatibility with polyfunctional styrene compounds, and resin agglomeration problems occur.
As is clear from the data of comparative example 2, comparative example 2 was free of polyfunctional styrene compound, and the dielectric constant Dk and the loss tangent Df at 10GHz were both significantly deteriorated, and the Tg of the laminate was significantly lowered, only 185℃was found, the heat resistance was insufficient, the time of delamination at 288℃was found to be only 18 minutes, and the copper-clad plate was exploded after tin immersion.
As is clear from the data of comparative example 3, the initiator of comparative example 3 uses only one high temperature initiator, and does not use a low temperature initiator, so that the product has excessive gummosis and poor appearance, and is difficult to prepare into a satisfactory product.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims (6)

1. A thermosetting resin composition containing a styrene compound is characterized by comprising the following raw material components in parts by weight: 15-50 parts of unsaturated triblock copolymer (a), 35-75 parts of polyfunctional styrene compound (b), 5-25 parts of auxiliary crosslinking agent (c), 0.2-3 parts of free radical polymerization initiator (d), 10-40 parts of flame retardant (e) and 50-100 parts of inorganic filler (f);
Wherein the unsaturated triblock copolymer has an ase:Sub>A-B-ase:Sub>A type block structure in which the ase:Sub>A block is ase:Sub>A polyalkenyl arene polymer comprising mono alkenyl arene units and the B block is ase:Sub>A non-hydrogenated poly acyclic conjugated diene polymer comprising polymerized units of at least one acyclic conjugated diene;
The radical polymerization initiator (d) includes a first radical initiator (d 1) having a half-life temperature of 80 to 120 ℃ for one hour and a second radical initiator (d 2) having a half-life temperature of 130 to 170 ℃ for one hour;
The first free radical initiator and the second free radical initiator can respectively initiate the crosslinking reaction of unsaturated double bonds in the resin composition at different temperatures; thus, the resin composition is partially crosslinked at the one-hour half-life temperature of the first free radical initiator, i.e., the first crosslinking temperature, and is further crosslinked at the one-hour half-life temperature of the second free radical initiator, i.e., the second crosslinking temperature;
The unsaturated triblock copolymer has a number average molecular weight Mn of 5,000-50,000g/mol as measured by gel permeation chromatography GPC, has narrow molecular weight control, and a ratio PDI of weight average molecular weight Mw to number average molecular weight Mn is less than or equal to 1.20, wherein the polyalkenyl arene structural unit accounts for 30-75% of the total mass of the unsaturated triblock copolymer;
The a block is a polyalkenyl arene polymer comprising at least high Tg monoalkenyl arene units having a Tg >100 ℃, wherein the a block is a polyalkenyl arene homopolymer having a GPC peak molecular weight Mp of less than 35,000 g/mol;
The B block has a high-reactivity structural unit, the side group has an unsaturated double bond structure, the poly-acyclic conjugated diene polymer is obtained through anionic polymerization, and the poly-acyclic conjugated diene polymer has a highly selective 1, 2-vinyl structural unit, wherein the 1, 2-vinyl polyolefin structure accounts for more than 85% of the mole ratio of the whole B block, and the GPC peak molecular weight Mp of the B block is more than 3,000g/mol and less than 30,000g/mol;
the molecular structure of the polyfunctional styrene compound (b) is shown in the following formula (1):
，
(1)
Wherein R represents a hydrocarbon skeleton, R 1 represents a C1-C20 hydrocarbon group, R 2,R3,R4 represents a hydrogen atom or a C1-C6 hydrocarbon group, R 2,R3,R4 may be the same or different, m is an integer of 1 to 4, and n is an integer of 2 or more;
the co-crosslinking agent (c) comprises divinylbenzene and/or triallyl isocyanurate;
the mass fraction of the resin composition is 0.2-3 parts by mass of the total mass of the free radical polymerization initiator;
the first and second radical initiators are each an organic peroxide or azo compound.
2. A styrene compound-containing thermosetting resin composition according to claim 1, wherein the a block comprises one or more of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, a-methylstyrene, vinyl-benzocyclobutene, vinylbiphenyl, adamantylstyrene, or 1, 1-diphenyl-ethylene; the B block comprises one or both of 1, 2-polybutadiene or 1, 2-polyisoprene.
3. A styrene-containing thermosetting resin composition according to claim 1, wherein said polyfunctional styrene compound (b) has a number average molecular weight of 1000g/mol or less,
The vinyl compound comprises any one or more of p, p ' -divinyl-1, 2-diphenyl ethane, m, m ' -divinyl-1, 2-diphenyl ethane, m, p ' -divinyl-1, 2-diphenyl ethane, p, p ' -divinyl-1, 2-diphenyl methane, m, m ' -divinyl-1, 2-diphenyl methane, m, p ' -divinyl-1, 2-diphenyl methane and p, p ' -divinyl-1, 2-diphenyl propane, m, m ' -divinyl-1, 2-diphenyl propane, m, p ' -divinyl-1, 2-diphenyl propane, wherein p, p ' represents para-position of benzene ring, m, m ' represents meta-position of benzene ring.
4. The thermosetting resin composition containing a styrene compound according to claim 1, wherein said flame retardant comprises one or more of decabromodiphenylethane, decabromodiphenylether, octabromodiphenylether, ethylene bis-tetrabromophthalimide;
The inorganic filler is a low-dielectric synthetic spherical silica filler, the filler is spherical silica filler with the surface treated by vinyl or allyl or (methyl) acrylic ester silane coupling agent, and the dielectric loss of the spherical silica filler is less than 0.0014 at the frequency of 10 GHz;
the average particle diameter D50 of the flame retardant and the inorganic filler is selected to be 0.5-5 mu m.
5. The method for preparing a styrene compound-containing thermosetting resin composition according to claim 1, wherein the unsaturated triblock copolymer (a) and the polyfunctional styrene compound (b) are dissolved in a solvent according to a formulation, then the auxiliary crosslinking agent (c) is added, the mixture is uniformly mixed and stirred, the free radical polymerization initiator (d) is added, and the styrene compound-containing thermosetting resin composition is obtained after dispersion treatment, and the flame retardant and the inorganic filler are added before the free radical polymerization initiator (d) is added.
6. The use of a thermosetting resin composition containing a styrene compound according to claim 1 for the manufacture of prepregs, metal foil-clad laminates and multilayer printed wiring boards.
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