CN112679936B - Thermosetting resin composition, resin glue solution containing thermosetting resin composition, prepreg, laminated board, copper-clad plate and printed circuit board - Google Patents
Thermosetting resin composition, resin glue solution containing thermosetting resin composition, prepreg, laminated board, copper-clad plate and printed circuit board Download PDFInfo
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- 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
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- 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
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- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
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- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/067—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of fibres or filaments
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
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- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5435—Silicon-containing compounds containing oxygen containing oxygen in a ring
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- 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
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Abstract
The invention relates to a thermosetting resin composition, and a resin glue solution, a prepreg, a laminated board, a copper-clad plate and a printed circuit board containing the thermosetting resin composition. The thermosetting resin composition comprises the following components: thermosetting polyphenyl ether resin, unsaturated styrene-butadiene resin, multifunctional vinyl aromatic copolymer, initiator, silane coupling agent and filler; the multifunctional vinyl aromatic copolymer is a copolymer obtained by copolymerizing a divinyl aromatic compound (a), styrene (b) and a monovinyl aromatic compound (c) except styrene; the amount of the polyfunctional vinyl aromatic copolymer is 5 to 25 parts by weight based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin. The plate prepared from the thermosetting resin composition provided by the invention has higher glass transition temperature, lower thermal expansion coefficient, and comprehensive properties of low dielectric constant, low dielectric loss, high flame retardance, high peel strength and the like.
Description
Technical Field
The invention relates to the technical field of communication materials, in particular to a thermosetting resin composition, and a resin glue solution, a prepreg, a laminated board, a copper-clad plate and a printed circuit board containing the thermosetting resin composition.
Background
In recent years, with the development of high performance, high functionality, and networking of computers and information communication devices, operating signals tend to be high frequency for high-speed transmission and processing of large-capacity information, and thus demands have been made on materials for circuit substrates, particularly those using broadband, such as mobile communication devices.
Conventionally, epoxy resins having excellent adhesion properties have been widely used as materials for printed circuit boards. However, epoxy resin circuit boards generally have high dielectric constants and dielectric loss tangents (dielectric constants of more than 4 and dielectric loss tangents of about 0.02), and are insufficient in high-frequency characteristics, and thus cannot meet the demand for higher signal frequencies. Therefore, it is necessary to develop a resin having excellent dielectric characteristics, i.e., a resin having a low dielectric constant and a low dielectric loss tangent. For a long time, the technical personnel in the field research thermosetting polyphenyl ether resin, bismaleimide resin, vinyl benzyl ether resin, hydrocarbon resin and the like with good dielectric property; as is well known, curable crosslinked polyolefin resins (hydrocarbon resins) containing 1, 2-position addition butadiene structures in the molecules have good dielectric properties (comparable to polytetrafluoroethylene resins) and good fluidity, and further attract a great deal of intensive research on the curable crosslinked polyolefin resins, but due to insufficient heat resistance, the curable crosslinked polyolefin resins cannot meet the process manufacturing requirements of high-density multilayer printed wiring boards.
In recent years, in the field of electronic devices for communication, consumer use, industrial use, and the like, there has been a tendency toward miniaturization and high density of mounting methods. The printed circuit board also needs to be pressed for multiple times to form a high-density high-multilayer printed circuit board, and the copper clad plate which is the raw material of the high-multilayer printed circuit board needs to have higher heat resistance, better dimensional stability and lower thermal expansion coefficient.
CN110776739A discloses a thermosetting resin composition for high-speed substrates, which is prepared by mixing 100 parts by mass of cyanate ester resin, 5-15 parts by mass of allyl compound, 50-120 parts by mass of bismaleimide resin, 65-110 parts by mass of styryl polyphenylene oxide and 0.1-0.5 part by mass of initiator. The thermosetting resin composition for the high-speed substrate and a solvent are uniformly mixed to prepare a resin solution with the solid content of 60-70%, glass fiber cloth is soaked in the resin solution and then baked for 4-7min at the temperature of 130-170 ℃ to prepare a prepreg, then 3-16 layers of prepregs are stacked and attached with copper foils on two sides, and the copper clad laminate for the high-speed substrate is prepared by curing in a hot press, so that the obtained copper clad laminate has good performance and strong practicability. However, the resin composition has a large thermal expansion coefficient, and is prone to causing a problem of layered plate explosion when a multilayer plate or a multi-layer laminated plate is manufactured, thereby causing a large risk of reliability of the plate.
CN104725828A discloses a resin composition and a prepreg and a laminate using the same. The resin composition comprises: a prepolymer of a vinyl thermosetting polyphenylene ether with a difunctional maleimide or a polyfunctional maleimide; a polyolefin resin. The vinyl thermosetting polyphenyl ether and bifunctional maleimide or multifunctional maleimide are adopted for prepolymerization, the problem of incompatibility of the bifunctional maleimide or the multifunctional maleimide, the vinyl thermosetting polyphenyl ether and polyolefin resin is solved, the mixed glue solution is uniform and consistent, the prepreg appearance is uniform, and no phase separation problem exists in a substrate resin area. However, the polyolefin resin used in this system has a drawback of insufficient heat resistance, and the glass transition temperature and thermal expansion properties of the sheet are still to be further improved.
Therefore, the art needs to provide a resin composition for copper clad laminate with higher heat resistance on the premise of ensuring the performance such as lower dielectric constant.
Disclosure of Invention
The invention aims to provide a thermosetting resin composition, and a plate prepared from the thermosetting resin composition has a higher glass transition temperature and a lower thermal expansion coefficient, so that the reliability of the plate is improved, and the plate can meet the use requirement of a high-density multilayer plate.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a thermosetting resin composition, which comprises the following components: thermosetting polyphenyl ether resin, unsaturated styrene-butadiene resin, multifunctional vinyl aromatic copolymer, initiator, silane coupling agent and filler;
the multifunctional vinyl aromatic copolymer is a copolymer obtained by copolymerizing a divinyl aromatic compound (a), styrene (b) and a monovinyl aromatic compound (c) except styrene;
the polyfunctional vinyl aromatic copolymer is used in an amount of 5 to 25 parts by weight, for example, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, etc., based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin.
According to the invention, a soluble multifunctional vinyl aromatic copolymer containing a plurality of structural units is added into a thermosetting polyphenyl ether resin and unsaturated styrene-butadiene resin system as a cross-linking agent, the multifunctional vinyl aromatic copolymer contains a large number of double bonds of divinylbenzene, can generate addition polymerization with the double bonds in main resin, improves the cross-linking density, can improve the Tg of a plate, contains a large number of benzene rings, has strong rigidity, and can reduce the Coefficient of Thermal Expansion (CTE) of the plate, thereby improving the reliability of the plate, enabling the plate to meet the use requirements of a high-density multilayer plate, and meanwhile, the plate has the comprehensive performances of low dielectric constant, low dielectric loss, high flame retardance, high peel strength and the like.
In addition, the amount of the polyfunctional vinyl aromatic copolymer of the present invention to be added must be controlled within 5 to 25 parts by weight in order to obtain a high glass transition temperature and a low thermal expansion coefficient while ensuring high peel strength, and if the amount is less than 5 parts by weight, the glass transition temperature is lowered and the thermal expansion coefficient is increased, and if the amount exceeds 25 parts by weight, the glass transition temperature of the sheet is lowered and the peel strength is also lowered.
In the present invention, polyfunctional means including at least two functional groups.
Preferably, in the polyfunctional vinyl aromatic copolymer, the molar ratio of the structural units derived from the divinyl aromatic compound (a) to the total structural units is 2 mol% to 95 mol%, such as 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol% or the like, and the molar ratio of the total of the structural units derived from the styrene (b) and the monovinyl aromatic compound (c) other than styrene is 5 mol% to 98 mol%, such as 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, or the like, 80 mol%, 85 mol%, 90 mol%, 95 mol%, etc.
Preferably, the structural unit derived from the divinylaromatic compound (a) includes the following structural unit (a1) and/or structural unit (a 2):
said R is a And R b Each independently selected from C6-C30 arylene groups (e.g., phenylene, biphenylene, naphthylene, phenanthrylene, etc.).
The polyfunctional vinyl aromatic copolymer crosslinking agent used in the present invention may be commercially available or may be synthesized according to the conventional technical knowledge in the art, and may be, for example only, a divinyl aromatic compound (a) copolymerized with styrene (b) and a monovinyl aromatic compound (c) other than styrene, wherein the structural unit formed by the divinyl aromatic compound (a) may include the structural unit (a1) and the structural unit (a 2).
Preferably, the structural element (a1) is in particular
Preferably, the structural element (a2) is in particular
Preferably, the polyfunctional vinyl aromatic copolymer comprises any one or at least two combinations (e.g., three combinations, four combinations, five combinations, or six combinations) of the following structural units:
wherein R is 1 And R 2 Each independently is a C6-C12 arylene radical, R 3 Is a hydrogen atom or a Cl-C12 hydrocarbon group. The hydrocarbon group includes an alkane group, an alkene group or an aromatic hydrocarbon group.
Preferably, the polyfunctional vinylaromatic copolymer has a number-average molecular weight of 600 to 20000g/mol, for example 1000g/mol, 2000g/mol, 4000g/mol, 6000g/mol, 8000g/mol, 10000g/mol, 12000g/mol, 14000g/mol, 16000g/mol, 18000g/mol, preferably 1000-. The number average molecular weight test method mentioned in the present invention is GB/T21863-.
Preferably, the thermosetting polyphenylene ether resin has a number average molecular weight of 500-10000g/mol, such as 1000g/mol, 2000g/mol, 3000g/mol, 4000g/mol, 5000g/mol, 6000g/mol, 7000g/mol, 8000g/mol, 9000g/mol, and the like.
Preferably, the thermosetting polyphenylene ether resin has a structure represented by the formula (1):
in formula (1), a and b are each independently an integer of 1 to 30, such as 2,4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, etc.;
in formula (1), Z has a structure represented by formula (2) or formula (3):
in the formula (3), A is selected from any one of C6-C30 arylene, C1-C10 alkylene or carbonyl, and R is 1 、R 2 And R 3 Each independently selected from a hydrogen atom or a C1-C10 alkyl group, said m being selected from integers from 0-10, such as 1,2, 3, 6, 8, 9, etc.;
wherein, the mark position of the wavy line represents a connecting bond;
in the formula (1), the- (-O-Y-) has a structure shown in a formula (4);
in the formula (4), R is 4 And R 6 Each independently selected from any one of a hydrogen atom, a halogen atom, C1-C10 alkyl or phenyl, and R is 5 And R 7 Each independently selected from any one of halogen atom, C1-C10 alkyl or phenyl;
in the formula (1), the- (-O-X-O-) -has a structure shown in a formula (5);
in the formula (5), R is 8 -R 15 Each independentlySelected from any one of hydrogen atom, halogen atom, C1-C10 alkyl or phenyl, and B is selected from C1-C10 alkylene, -O-, -CO-, -SO-, -CS-or-SO 2 Any one of the above-mentioned.
Preferably, the unsaturated styrene-butadiene resin is used in an amount of 25 to 250 parts by weight, for example, 30 parts by weight, 50 parts by weight, 60 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, 200 parts by weight, 220 parts by weight, 240 parts by weight, etc., based on 100 parts by weight of the thermosetting polyphenylene ether resin.
Preferably, the unsaturated styrene-butadiene resin is a copolymer of butadiene and styrene, and the weight ratio of the butadiene to the total amount of butadiene and styrene is not less than 20%, for example, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 40%, 42%, 44%, 46%, 48%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc., preferably not less than 30%, more preferably 70%.
Preferably, the weight ratio of 1-and 2-position vinyl groups to all vinyl groups in the unsaturated styrene-butadiene resin is not less than 40%, for example, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, etc., and more preferably not less than 70%.
Preferably, the initiator is used in an amount of 0.5 to 3 parts by weight, for example, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight, etc., based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin.
Preferably, the initiator is a free radical initiator, preferably dicumyl peroxide, tert-butyl peroxybenzoate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, di- (tert-butylperoxyisopropyl) benzene, peroxy (2, 4-dichlorobenzoyl), 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane, tert-butyl peroxy-2-ethylhexylcarbonate, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) -3-hexyne, butyl 4, 4-bis (tert-butylperoxy) valerate, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 3,5,7, 7-pentamethyl-1, 2, 4-trioxepane, di-tert-butyl peroxide or tert-butyl cumyl peroxide, or a combination of at least two thereof.
Preferably, the half-life temperature of the free radical initiator is ≥ 130 deg.C, e.g. 131 deg.C, 135 deg.C, 138 deg.C, 140 deg.C, 145 deg.C, etc.
Preferably, the silane coupling agent is used in an amount of 0.5 to 1.5 parts by weight, for example, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, 1 part by weight, 1.1 part by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, etc., based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin.
Preferably, the filler is used in an amount of 20 to 50 parts by weight, for example, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 38 parts by weight, 40 parts by weight, 42 parts by weight, 44 parts by weight, 46 parts by weight, 48 parts by weight, etc., based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin.
Preferably, the filler comprises an organic filler and/or an inorganic filler.
Preferably, the inorganic filler includes any one or a combination of at least two of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, alumina, barium sulfate, talc, calcium silicate, calcium carbonate, or mica.
Preferably, the organic filler comprises any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder, polyetherimide powder, polyphenylene oxide powder or polyether sulfone powder.
Preferably, the present invention may further add flame retardants, other crosslinking agents, auxiliaries, and the like, as needed.
Another object of the present invention is to provide a resin coating solution obtained by dissolving or dispersing the thermosetting resin composition according to the first object in a solvent.
The solvent in the present invention is not particularly limited, and alcohols such as methanol, ethanol and butanol, alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol and butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and ethoxyethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide and N, N-dimethylacetamide can be used. The above solvents may be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferable. The addition amount of the solvent is selected by the skilled person according to the experience of the person in the art, so that the resin glue solution can reach the viscosity suitable for use.
It is a further object of the present invention to provide a prepreg comprising a reinforcing material and the thermosetting resin composition for one of the objects of being impregnated and dried and then adhering thereto.
In the invention, the reinforcing material can be organic fiber cloth, inorganic fiber woven cloth or non-woven cloth; wherein the organic fiber is aramid non-woven fabric; the inorganic fiber woven cloth is E-glass fiber cloth, D-glass fiber cloth, S-glass fiber cloth, T-glass fiber cloth, NE-glass fiber cloth or quartz cloth. The thickness of the reinforcing material is 0.01-0.2mm, such as 0.02mm, 0.05mm, 0.08mm, 0.1mm, 0.12mm, 0.15mm, 0.18mm, and the like. And the reinforcing material is preferably subjected to fiber opening treatment and silane coupling agent surface treatment; the silane coupling agent is any one or a mixture of at least two of epoxy silane coupling agent, amino silane coupling agent or vinyl silane coupling agent.
It is a fourth object of the present invention to provide a laminate comprising at least one third of said prepregs.
The fifth purpose of the invention is to provide a copper-clad plate, which contains at least one third of the prepreg and metal foils coated on one side or two sides of the laminated prepreg.
Preferably, the metal foil is a copper foil, a nickel foil, an aluminum foil, or a SUS foil, etc.
The sixth purpose of the invention is to provide a printed circuit board, which comprises the laminated board of the fourth purpose, the copper-clad plate of the fifth purpose or the prepreg of the third purpose.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the soluble multifunctional vinyl aromatic copolymer is added into a thermosetting polyphenyl ether resin and unsaturated styrene-butadiene resin system as a cross-linking agent, so that the glass transition temperature of the board can be effectively increased, and the thermal expansion coefficient is reduced, thereby improving the reliability of the board, enabling the board to meet the use requirements of high-density multilayer boards, and meanwhile, the board has the comprehensive properties of low dielectric constant, low dielectric loss, high flame retardance, high peel strength and the like.
The copper-clad plate provided by the invention has the glass transition temperature of 190-210 ℃, the CTE (Z axis) alpha _1| of 22-32, the alpha _2| of 149-166, the integral expansion rate of 50-260 ℃, the Dk of about 3.6, the Df of about 0.002, the peel strength of 0.8-1.1N/mm and the flame retardant grade of V-0.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw materials used in the following examples and comparative examples are shown in table 1.
TABLE 1
Examples 1 to 5 and comparative examples 1 to 4
The thermosetting resin composition is prepared according to the components shown in the table 2, and the copper-clad plate sample is manufactured according to the following copper-clad plate manufacturing method:
(1) uniformly mixing the components in the formula amount in the thermosetting resin composition in toluene, and uniformly dispersing at room temperature to obtain a resin glue solution with a solid content of 65%;
(2) impregnating the resin glue solution obtained in the step (1) with a reinforcing material (glass fiber cloth), and baking the resin glue solution in an oven at 155 ℃ for 5min to realize curing to obtain a prepreg; and (3) placing the prepreg between two copper foils, laminating and curing for 2h at 210 ℃ and 2.1MPa in a hot press to obtain the copper-clad plate.
Performance testing
The following performance tests were performed on the copper-clad plates obtained in the above examples and comparative examples:
(1) Dk/Df test method: the IPC-TM-6502.5.5.5 standard method is adopted, and the frequency is 10 GHz.
(2) The flame retardant property test method comprises the following steps: according to UL94 "50W (20mm) vertical burning test: v-0, V-1 and V-2' test methods, V-0 is determined to be flame retardant.
(3) Tg (dma) test method: the IPC-TM-6502.4.24.4 standard method is adopted.
(4) CTE (Z axis) test method: using a thermomechanical analyzer (TMA), the IPC-TM-6502.4.24 standard method was used.
(5) Copper foil Peel Strength (PS) test: IPC-TM-650; peel strength tester.
The results of the above performance tests are shown in table 2.
TABLE 2
As can be seen from the data in Table 2, the copper-clad plate prepared from the resin composition provided by the invention has higher glass transition temperature, lower thermal expansion coefficient, and simultaneously has the comprehensive properties of low dielectric constant, low dielectric loss, high flame retardance, high peel strength and the like.
Example 1 showed less difference in electrical properties compared to comparative example 2, with an overall CTE reduction of 16.7% due to an increase in tg (dma) of about 30 ℃, and example 2 showed less difference in electrical properties compared to comparative example 2, with an overall CTE reduction of 45.8% due to an increase in tg (dma) of about 40 ℃. Therefore, the multifunctional vinyl aromatic copolymer is added, so that the glass transition temperature can be effectively increased, the thermal expansion coefficient can be reduced, negative effects on the electrical property can be avoided, and the multifunctional vinyl aromatic copolymer adopted by the invention is proved to have advantages compared with the prior art without the multifunctional vinyl aromatic copolymer.
Example 3 when the multifunctional vinyl aromatic copolymer is added in an amount exceeding 25 parts by weight, Tg (DMA) thereof is decreased from 208.2 ℃ to 200.2 ℃ by about 8 ℃ and PS is decreased from 0.94N/mm to 0.83N/mm, as compared with comparative example 4. It is thus demonstrated that the amount of polyfunctional vinyl aromatic copolymer added must be controlled within the specified range of the present invention to provide copper clad laminate with higher glass transition temperature and lower coefficient of thermal expansion without affecting other properties.
Compared with the comparative example 3, the comparative example 3 adopts the same amount of divinylbenzene as the crosslinking agent, and the peel strength of the obtained copper-clad plate is 0.76N/mm, which is reduced by about 22 percent compared with the 0.93N/mm of the example.
Compared with the comparative example 5, the comparative example 5 selects the same amount of polybutadiene, the difference between the electrical property and Tg of the obtained copper-clad plate is not large compared with the example 3, but the overall expansion rate in CTE is increased from 1.3% to 1.6% and increased by 23% compared with the example, and the heat resistance is obviously poor.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (22)
1. A thermosetting resin composition characterized by comprising the following components: thermosetting polyphenyl ether resin, unsaturated styrene-butadiene resin, multifunctional vinyl aromatic copolymer, initiator, silane coupling agent and filler;
the multifunctional vinyl aromatic copolymer is a copolymer obtained by copolymerizing a divinyl aromatic compound (a), styrene (b) and a monovinyl aromatic compound (c) except styrene;
the amount of the polyfunctional vinyl aromatic copolymer is 5 to 25 parts by weight based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin;
the amount of the thermosetting polyphenyl ether resin is 100 parts by weight, and the amount of the unsaturated styrene-butadiene resin is 25-100 parts by weight;
the weight ratio of 1, 2-vinyl in the unsaturated styrene-butadiene resin to all vinyl is more than or equal to 40 percent;
the amount of the initiator is 0.5-3 parts by weight based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin.
2. The thermosetting resin composition claimed in claim 1, wherein the molar ratio of the structural unit derived from the divinylaromatic compound (a) to the total structural unit in the polyfunctional vinyl aromatic copolymer is 2 to 95 mol%, and the molar ratio of the structural units derived from the styrene (b) and the monovinylaromatic compound (c) other than styrene to the total structural unit is 5 to 98 mol%.
3. The thermosetting resin composition according to claim 1, wherein the structural unit derived from the divinylaromatic compound (a) comprises the following structural unit (a1) and/or structural unit (a 2):
the R is a And R b Each independently selected from C6-C30 arylene.
4. The thermosetting resin composition as claimed in claim 1, wherein the number average molecular weight of the polyfunctional vinyl aromatic copolymer is 600-.
5. The thermosetting resin composition as claimed in claim 1, wherein the number average molecular weight of the thermosetting polyphenylene ether resin is 500-10000 g/mol.
6. The thermosetting resin composition as claimed in claim 1, wherein the thermosetting polyphenylene ether resin has a structure represented by the formula (1):
in the formula (1), a and b are each independently an integer of 1 to 30;
in formula (1), Z has a structure represented by formula (2) or formula (3):
in the formula (3), A is selected from any one of C6-C30 arylene, C1-C10 alkylene or carbonyl, and R is 1 、R 2 And R 3 Each independently selected from a hydrogen atom or a C1-C10 alkyl group, and m is selected from an integer of 0-10;
wherein, the mark position of the wavy line represents a connecting bond;
in the formula (1), the
Has a structure represented by formula (4);
in the formula (4), R is 4 And R 6 Each independently selected from any one of a hydrogen atom, a halogen atom, C1-C10 alkyl or phenyl, and R is 5 And R 7 Each independently selected from any one of halogen atom, C1-C10 alkyl or phenyl;
in the formula (1), the
Has a structure represented by formula (5);
in the formula (5), R is 8 -R 15 Each independently selected from any one of hydrogen atom, halogen atom, C1-C10 alkyl or phenyl, and B is selected from C1-C10 alkylene, -O-, -CO-, -SO-, -CS-or-SO 2 Any one of the above-mentioned.
7. The thermosetting resin composition claimed in claim 1, wherein the unsaturated styrene-butadiene resin is a copolymer of butadiene and styrene, and the weight ratio of butadiene to the total amount of butadiene and styrene is not less than 20%.
8. The thermosetting resin composition claimed in claim 7, wherein the butadiene is not less than 30% by weight of the total amount of the butadiene and styrene.
9. The thermosetting resin composition recited in claim 7, wherein the butadiene is 70% by weight of the total amount of butadiene and styrene.
10. The thermosetting resin composition of claim 1, wherein the initiator is a free radical initiator.
11. The thermosetting resin composition of claim 10, wherein said initiator is dicumyl peroxide, t-butyl peroxybenzoate, 2, 5-bis (2-ethylhexanoylperoxy) -2, 5-dimethylhexane, bis- (t-butylperoxyisopropyl) benzene, bis (2, 4-dichlorobenzoyl) peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, t-butyl peroxy-2-ethylhexylcarbonate, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) -3-hexyne, 4-bis (t-butylperoxy) valerate, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 3,3,5,7, 7-pentamethyl-1, 2, 4-trioxepane, di-tert-butyl peroxide or tert-butyl cumyl peroxide, or a combination of at least two of them.
12. The thermosetting resin composition of claim 10, wherein the half-life temperature of the free radical initiator is 130 ℃ or more.
13. The thermosetting resin composition claimed in claim 1, wherein the silane coupling agent is used in an amount of 0.5 to 1.5 parts by weight based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin.
14. The thermosetting resin composition claimed in claim 1, wherein the filler is used in an amount of 20 to 50 parts by weight based on 100 parts by weight of the sum of the amounts of the thermosetting polyphenylene ether resin and the unsaturated styrene-butadiene resin.
15. The thermosetting resin composition of claim 1, wherein the filler comprises an organic filler and/or an inorganic filler.
16. The thermosetting resin composition of claim 15, wherein the inorganic filler comprises any one or a combination of at least two of crystalline silica, fused silica, spherical silica, hollow silica, glass frit, aluminum nitride, boron nitride, silicon carbide, aluminum hydroxide, titanium dioxide, strontium titanate, barium titanate, alumina, barium sulfate, talc, calcium silicate, calcium carbonate, or mica.
17. The thermosetting resin composition of claim 15, wherein the organic filler comprises any one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder, polyetherimide powder, polyphenylene oxide powder, or polyethersulfone powder.
18. A resin cement obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 17 in a solvent.
19. A prepreg comprising a reinforcing material and a thermosetting resin composition according to any one of claims 1 to 17 attached thereto by impregnation and drying.
20. A laminate comprising at least one prepreg according to claim 19.
21. A copper-clad plate characterized in that it comprises at least one prepreg according to claim 19 and a metal foil coated on one or both sides of the laminated prepreg.
22. A printed circuit board comprising the laminate of claim 20 or the copper clad laminate of claim 21 or the prepreg of claim 19.
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| CN202011536162.9A CN112679936B (en) | 2020-12-23 | 2020-12-23 | Thermosetting resin composition, resin glue solution containing thermosetting resin composition, prepreg, laminated board, copper-clad plate and printed circuit board |
| PCT/CN2021/070438 WO2022134215A1 (en) | 2020-12-23 | 2021-01-06 | Thermosetting resin composition, resin adhesive liquid containing same, prepreg, laminate, copper clad laminate and printed circuit board |
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| JP2007262191A (en) * | 2006-03-28 | 2007-10-11 | Nippon Steel Chem Co Ltd | Flame-retardant curable resin composition |
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| CN109385018A (en) * | 2017-08-04 | 2019-02-26 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg and metal-clad laminate using its production |
| CN109385021A (en) * | 2017-08-04 | 2019-02-26 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg and metal-clad laminate using its production |
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