WO2018120589A1 - 一种改性聚苯醚树脂及其应用 - Google Patents

一种改性聚苯醚树脂及其应用 Download PDF

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Publication number
WO2018120589A1
WO2018120589A1 PCT/CN2017/084317 CN2017084317W WO2018120589A1 WO 2018120589 A1 WO2018120589 A1 WO 2018120589A1 CN 2017084317 W CN2017084317 W CN 2017084317W WO 2018120589 A1 WO2018120589 A1 WO 2018120589A1
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Prior art keywords
polyphenylene ether
resin composition
modified polyphenylene
resin
ether resin
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PCT/CN2017/084317
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English (en)
French (fr)
Inventor
孟运东
徐莹
方克洪
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广东生益科技股份有限公司
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Publication of WO2018120589A1 publication Critical patent/WO2018120589A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides

Definitions

  • the invention relates to the technical field of copper clad laminates, in particular to a modified polyphenylene ether resin and an application thereof.
  • Polyphenylene ether resin has good heat resistance, dielectric properties and toughness, and has a good application prospect in composite materials such as laminates.
  • the compatibility is poor and the phase separation is easy, so the application of the polyphenylene ether has various difficulties.
  • solutions have been proposed in several patents, but there are deficiencies in terms of feasibility and cost.
  • CN1458963A mentions that PPO and a trialkyl cyanurate cured product form an IPN structure in which a side chain of a PPO structure linked to a benzene ring is H or may be different from 1 to 3 hydrocarbon groups; CN102206415 Mention is made of a cyanate ester, an oxynitride compound and a polyphenylene ether, the polyphenylene ether used in the structure having a H or a methyl group in its side chain.
  • the groups of the side chains in many patents are generally defined as H or a group of 1 to 3 hydrocarbons, or are not limited.
  • polyphenylene ether resins have poor compatibility with thermosetting resins such as epoxy resins, and there are often phase-separated "islands" phenomenon in the cured product, which affects the uniformity of the resin matrix, electrical properties, heat resistance, etc. Negative effects.
  • CN102702680A discloses a composition of a polyphenylene ether and an epoxy resin, wherein the polyphenylene ether used has a small molecular weight and has good compatibility with an epoxy resin, but its Df is high;
  • CN103102484A mentions a kind a crosslinkable polyphenylene ether resin having a H chain or a group of 1 to 3 hydrocarbons linked to a benzene ring in a side chain thereof; and a terminal epoxy group-modified polyphenylene ether resin mentioned in CN105419348A
  • the polyphenylene ether structure side chain position is H or 1 to 8 hydrocarbon groups, but the side chain position of hydrocarbon hydrogenation is not described.
  • the existence of the group of compounds, and changing the hydrocarbon group of the side chain in the middle portion of the structure of the commonly used polyphenylene ether resin is a relatively complicated process.
  • the molecular weight of the polyphenylene ether is generally reduced, or a reactive group is introduced at the end group of the polyphenylene ether to improve the compatibility of the polyphenylene ether with the thermosetting resin, but the dielectric properties of the sheet are negative. Impact, and the improvement is not ideal.
  • one of the objects of the present invention is to provide a modified polyphenylene ether resin having a long carbon chain structure, which not only can increase the compatibility between polyphenylene ether and other resins, but also contribute to the reduction of lamination.
  • the dielectric constant and loss of the sheet, and the adhesion of the resin system to the metal foil can be improved.
  • the inventors conducted intensive studies and found that by using a polyphenylene ether resin having at least one group of hydrocarbons having a carbon element of more than 3 in the structure, and an epoxy resin, a curing agent, The above object can be attained by a thermosetting resin composition obtained by appropriately mixing a curing accelerator and other optional materials.
  • a modified polyphenylene ether resin comprising at least one group of hydrocarbons having a carbon element greater than 3 in the modified polyphenylene ether resin structure.
  • the invention adopts a polyphenylene ether resin containing at least one hydrocarbon group of carbon elements greater than 3 in the structure, which can not only increase the compatibility between the polyphenylene ether and other resins, but also the phase separation "island" phenomenon of the resin system. There is a significant improvement, and it helps to reduce the dielectric constant and loss of the laminated sheet, and can improve the adhesion of the resin system to the metal foil and maintain the heat resistance of the sheet.
  • the polyphenylene ether resin structure comprises at least one group of hydrocarbons having a carbon element greater than 3, for example, a group, two or more groups of hydrocarbons having a carbon element greater than 3, wherein
  • the number of carbon elements of the hydrogen compound group may be, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.
  • the polyphenylene ether resin structure preferably contains at least one group of hydrocarbons having a carbon element of more than 6, and further preferably contains at least one group of hydrocarbons having a carbon element of greater than 9.
  • the present invention adopts the above-mentioned preferred polyphenylene ether resin, which unexpectedly improves the problem that the polyphenylene ether has poor compatibility with thermosetting resins such as epoxy resin and cyanate ester, and reduces or eliminates the phase separation "island" of the resin system.
  • the particle size increases the bonding force between the polyphenylene ether and other resins, improves the uniformity of the resin matrix of the sheet, improves the dielectric properties of the sheet, and improves the peel strength and impact resistance of the sheet.
  • the modified polyphenylene ether resin is obtained by reacting a phenolic compound having a long carbon chain with a polyphenylene ether resin under the action of a peroxide or the like, wherein a phenolic compound having a long carbon chain means having
  • the compound having a long carbon chain and a phenolic hydroxyl group preferably has a structural formula as shown in formula (I) or (II):
  • R 1 , R 2 , R 3 or R 4 are each independently H or C k H j , k is an integer of 1 to 20, and j is an integer of 2k-3 to 2k+1; in the formula (I), At least one of R 1 and R 2 is C m H n , and m is an integer of 4 to 20, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 , 18, 19 or 20, n is an integer of 2m-3 to 2m+1; in the formula (II), at least one of R 1 , R 2 , R 3 or R 4 is C m H n and m is 4-20 An integer such as 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, n is an integer from 2m to 2m+1.
  • thermosetting resin composition comprising the following components in weight percent:
  • (C) curing agent 5% to 50%
  • the percentages of the components (A), (B), (C), and (D) are solvent-free.
  • the total weight of the modified polyphenylene ether resin is from 5% to 45%, such as 5%, based on the total of (A), (B), (C) and (D). 6%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 35%, 38%, 40%, 42% or 45%, and the above
  • the specific point values between the numerical values are limited to the length and for the sake of brevity, the present invention is no longer exhaustively enumerated.
  • the molecular weight of the low molecular weight polyphenylene ether resin is from 1,000 to 7,000, for example, 1,000. , 2000, 3000, 4000, 5000, 6000 or 7000, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention no longer exhaustively enumerates the specific point values included in the range, preferably 1500. ⁇ 4000; Meanwhile, the present invention may further comprise a low molecular weight modified polyphenylene ether resin having a hydroxyl group, an epoxy group or an amine group at both ends in the structure.
  • the epoxy resin composition has a weight percentage of 15% to 60%, for example, 15%, 16 based on the total of (A), (B), (C) and (D). %, 18%, 20%, 22%, 25%, 28%, 30%, 35%, 40%, 42%, 45%, 50%, 52%, 55%, 58% or 60%, and the above values
  • the specific point values are not limited to the specific point values included in the scope.
  • the epoxy resin composition comprises any one or a mixture of at least two of a bisphenol A type, a bisphenol F type, a bicyclic decadiene type or a biphenyl type epoxy resin, of which typical but not The limiting mixtures are bisphenol A type and bisphenol F type epoxy resins, bicyclic decadiene type and biphenyl type epoxy resins, and the like.
  • the epoxy resin composition in the present invention preferably contains an epoxy resin having a low number average molecular weight, and the number average thereof
  • the molecular weight is preferably from 200 to 600, such as 200, 250, 300, 350, 400, 500 or 600, and the specific point values between the above values, which are limited in scope and for the sake of brevity, the present invention is not exhaustively enumerated.
  • the specific point value included; the epoxy resin accounts for 10% to 90% by weight of all epoxy resins, for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90%, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range, preferably 30% to 70%.
  • the epoxy resin composition of the present invention may further comprise an epoxy resin having a carbon chain structure in a side chain and an epoxy resin having a better solubility in toluene.
  • the total weight of the curing agent is from 5% to 50%, such as 5%, 6%, and 8 based on the total of (A), (B), (C), and (D). %, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 42%, 45%, 48% or 50%, and between the above values
  • the specific point values limited by the length and for the sake of brevity, are not exhaustively enumerated.
  • the curing agent comprises any one or a mixture of at least two of an amine curing agent, an acid anhydride curing agent, an imidazole curing agent, a phenol resin curing agent, a cyanate ester or a benzoxazine resin.
  • an amine curing agent an acid anhydride curing agent, an imidazole curing agent, a phenol resin curing agent, a cyanate ester or a benzoxazine resin.
  • Typical but non-limiting mixtures thereof are amine curing agents and acid anhydride curing agents, acid anhydride curing agents and imidazole curing agents, cyanate esters and benzoxazine resins, and the like.
  • the weight percentage of the curing accelerator is 0.01% to 3%, for example, 0.01%, 0.05%, based on the total of (A), (B), (C), and (D). 0.1%, 0.5%, 0.6%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8% or 3%, and specific points between the above values Values, limited by length and for the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.
  • the curing accelerator is 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, a complex of tri-n-butylamine, triphenylphosphine, boron trifluoride or zinc, copper, iron, tin, cobalt, aluminum in octanoic acid, acetylacetone, naphthenic acid, salicylic acid or stearate Any one or a mixture of at least two, wherein a typical but non-limiting mixture is 2-methylimidazole and 2-phenylimidazole, 2-ethyl-4-methylimidazole and tri-n-butylamine, naphthenic acid And salicylic acid and so on.
  • the thermosetting resin composition further comprises (E) filler in an amount of 5% to 45% by weight; that is, the weight percentage of the filler is 5% to 45% based on the total amount of the thermosetting resin composition. , for example, 5%, 6%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 42% or 45%, and the above values
  • the specific point values are not limited to the specific point values included in the scope.
  • the filler may be selected from an organic filler or an inorganic filler, wherein the inorganic filler may be selected from any one of spherical silicon micropowder, fused silica micropowder, aluminum hydroxide, boehmite, talc or hollow glass beads. Or a mixture of at least two, the organic filler may be selected from the group consisting of polytetrafluoroethylene powder and/or core-shell rubber.
  • the thermosetting resin composition further comprises (F) a flame retardant: 5% to 25% by weight; that is, the weight percentage of the flame retardant is 5 based on the total amount of the thermosetting resin composition. % to 25%, such as 5%, 6%, 8%, 10%, 12%, 13%, 14%, 15%, 18%, 20%, 22%, 24% or 25%, and between the above values
  • a flame retardant 5% to 25% by weight; that is, the weight percentage of the flame retardant is 5 based on the total amount of the thermosetting resin composition.
  • % to 25% such as 5%, 6%, 8%, 10%, 12%, 13%, 14%, 15%, 18%, 20%, 22%, 24% or 25%, and between the above values
  • the specific point values are limited to the length and for the sake of brevity, the present invention is no longer exhaustive to enumerate the specific point values included in the range.
  • the flame retardant may be selected from the group consisting of decabromodiphenyl ether, decabromodiphenylethane, ethylene bistetrabromophthalimide, melamine phosphate, melamine polyphosphate, and dimelamine coke.
  • Phosphate tris(tribromophenyl)cyanate, tris(2,6-dimethylphenyl)phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro- 9-oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene, 10-phenyl-9,10-dihydro-9-oxygen Any one or at least two of a hetero-10-phosphaphenanthrene-10-oxide or a phosphazene compound Mixtures, of which typical but non-limiting mixtures are: decabromodiphenyl ether and decabromodiphenylethane, ethylene bistetrabromophthalimide and melamine phosphate, 10-phenyl-9,10 - Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphazene compound, and the like.
  • composition means that it may include other components in addition to the components, and these other components impart different characteristics to the thermosetting resin composition.
  • the "comprising” described in the present invention may also be replaced by a closed “for” or “consisting of”.
  • thermosetting resin composition may further contain various additives or auxiliary agents, and specific examples thereof include a silane coupling agent, a filler dispersant, an antifoaming agent, an antioxidant, a heat stabilizer, and an antistatic agent.
  • additives or adjuvants may be used singly or in combination of two or more.
  • thermosetting resin composition of the present invention is a conventional technical means in the art, which is: firstly, the solid matter is put in, then the liquid solvent is added, and the mixture is stirred until the solid matter is completely dissolved, and then the liquid resin and the accelerator are added. Continue to stir evenly.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, and butyl.
  • Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate a nitrogen-containing solvent such as N,N-dimethylformamide or N,N-dimethylacetamide.
  • the above solvents may be used singly or in combination of two or more. Preference is given to ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone and cyclohexanone.
  • the amount of the solvent to be added is selected by those skilled in the art based on his own experience, so that the resin glue can reach a viscosity suitable for use.
  • the present invention also provides a resin glue obtained by dissolving or dispersing a thermosetting resin composition as described above in a solvent.
  • the present invention also provides a prepreg which is obtained by impregnating a base material with a resin glue as described above. Get it dry.
  • the prepreg of the present invention comprises a reinforcing material and a thermosetting resin composition as described above which is impregnated and adhered to the reinforcing material after drying.
  • the reinforcing material to be used is not particularly limited and may be an organic fiber, an inorganic fiber woven cloth or none. Woven cloth.
  • the organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth.
  • the thickness of the reinforcing material is not particularly limited, and the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably the fiber-opening treatment and the silane coupling agent are considered.
  • the silane coupling agent is preferably any one or at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent.
  • the prepreg is obtained by impregnating the above-mentioned thermosetting resin composition by baking the above-mentioned thermosetting resin composition at 100 to 250 ° C for 1 to 15 minutes.
  • the copper-clad laminate for a printed circuit board of the present invention comprises a laminate obtained by bonding two or more sheets of bonding sheets by heat and pressure, and bonded to one or both sides of the laminate.
  • the above copper foil; the copper clad laminate is laminated with two sheets of the above-mentioned bonding sheet and two sheets of one ounce (35 ⁇ m thick) copper foil, laminated by a hot press, thereby being pressed into a double
  • the copper-clad laminate is required to meet the following requirements: 1.
  • the heating rate of the lamination is usually controlled at 1.0-3.0 ° C/min when the temperature is 80-160 ° C;
  • the pressure of the lamination is set.
  • the full pressure is applied, and the full pressure is about 300 psi. 3.
  • the temperature of the control material is 185 ° C, and the temperature is kept for 90 min;
  • the copper foil, nickel foil, aluminum foil, SUS foil, etc. may be used, and the material thereof is not limited.
  • the present invention has at least the following beneficial effects:
  • the modified polyphenylene ether resin provided by the invention has at least one group of hydrocarbons with carbon elements greater than 3, which can not only increase the compatibility between the polyphenylene ether and other resins, but also the phase separation "island” of the resin system.
  • Significant improvement in the phenomenon the result of the largest phase separation "island” size shows no phase separation or ⁇ 5 ⁇ m; It helps to reduce the dielectric constant and loss of the laminated sheet, wherein the Dk value is in the range of 3.6 to 3.9, the Df value is between 0.006 and 0.008, the peel strength can reach 1.0 or more, and the adhesion of the resin system to the metal foil can be improved.
  • the knot maintains the heat resistance of the sheet, and the manufacturing process is simple and easy to implement.
  • the parts represent parts by weight, and the % represents "% by weight”.
  • the precipitate was dried at 100 ° C in a forced air oven to obtain a low molecular weight modified polyphenylene ether resin.
  • the number average molecular weight (Mn) of the resin was measured using toluene as a mobile phase, and the results are shown in Table 1.
  • the modified polyphenylene ether, epoxy resin and cyanate resin obtained in the preparation example are sufficiently dissolved in toluene (Dicy is sufficiently dissolved in DMF), and then promoted with 2 ethyl 4-methylimidazole and zinc isooctanoate. (The kinds and the parts are shown in Table 2) The mixture was uniformly mixed to obtain a toluene solution of the polyphenylene ether resin composition.
  • the NE type glass fiber cloth (Nitto Spin Co., Ltd., NEA2116) was immersed in the resin composition, and dried at 155 ° C for 2 to 10 minutes to remove the solvent to make the volatile matter less than 1%, and the gel time of the resin was 150 s to 200 s. A prepreg having a resin content of about 55% was obtained.
  • a reversed copper foil of HOz was coated on both sides of the four overlapping prepregs, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 min to obtain a double-sided copper clad laminate.
  • the modified polyphenylene ether, epoxy resin and cyanate resin obtained in the preparation example are sufficiently dissolved in toluene, and then mixed with a promoter such as 2 ethyl-4methylimidazole and zinc isooctanoate, and then added with filler and hindrance.
  • the fuel (the type and the number of parts are shown in Table 3) were uniformly dispersed by stirring and high-speed shearing to obtain a toluene solution of the polyphenylene ether resin composition.
  • the NE type glass fiber cloth (Nitto Spin Co., Ltd., NEA2116) was immersed in the resin composition, and dried at 155 ° C for 2 to 10 minutes to remove the solvent to make the volatile matter less than 1%, and the gel time of the resin was 150 s to 200 s. A prepreg having a resin content of about 55% was obtained.
  • a reversed copper foil of HOz was coated on both sides of the four overlapping prepregs, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 min to obtain a double-sided copper clad laminate.
  • Tg Glass transition temperature: using dynamic mechanical analysis (DMA) test, the heating rate is 20 ° C / min;
  • Td Thermal weight loss temperature
  • Peel strength refers to the tensile force required to peel off the copper clad plate per mm of copper foil at room temperature
  • Polyphenylene ether number average molecular weight after low molecular weight Mn The toluene solution of the modified polyphenylene ether obtained in the preparation example was tested by GPC, and the number average molecular weight (Mn) of the main peak position of the GPC spectrum was taken, and the mobile phase was tested to be toluene.
  • Examples 1 to 9 and 10 to 14 obtained the resin composition obtained by using the modified polyphenylene ether resin of the present invention, and the results of the maximum phase separation "islands" showed no phase separation or 5 ⁇ m or less.
  • the modified polyphenylene ether resin of the present invention has good compatibility with other resins; and in Comparative Examples 1 to 3 and 4 to 6, unmodified low molecular weight polyphenylene ether SA120 or low molecular weight poly is used.
  • the resin composition obtained from phenyl ether SA90 showed a maximum phase separation "islands" size of at least 10 ⁇ m, indicating that the compatibility between the unmodified polyphenylene ether resin and other resins was poor.
  • the obtained sheet had a Dk value of 3.6 to 3.9 and a Df value of 0.006 to 0.008, which was significantly lower than that of Comparative Examples 1 to 3 and 4 to 6.
  • the Dk values of 3.9 to 4.1 and Df values of 0.009 to 0.012 indicate that the dielectric properties are superior to those of Comparative Examples 1 to 3 and 4 to 6; in addition, the peel strength of the sheets obtained in Examples 1 to 9 can reach 1.0 or more.
  • the peel strength (0.5 to 0.8) of the comparative examples 1 to 3 was significantly higher, and the peel strength in the sheets obtained in Examples 10 to 14 was further between 0.8 and 1.1, which was significantly higher than the peel strength in the comparative examples 4 to 6 (0.3 to).
  • the resin composition obtained by using the modified polyphenylene ether resin of the present invention not only enhances the compatibility with other resin systems, but also effectively improves the dielectric properties of the sheet and improves the dielectric properties.
  • the peel strength and impact resistance of the sheet also maintain the heat resistance of the sheet such as Tg and Td.

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Abstract

本发明涉及一种改性聚苯醚树脂及其应用，该改性聚苯醚树脂具有长碳链结构，其包含至少一组碳元素大于3的碳氢化合物群。本发明通过采用结构中包含至少一组碳元素大于3的碳氢化合物群的改性聚苯醚树脂，不仅可以增加聚苯醚与其他树脂之间的相容性，对树脂体系的分相"海岛"现象有明显的改善，而且有助于降低层压板材的介电常数和损耗，并且可以提高树脂体系对金属箔的粘结性，保持了板材的耐热性能。

Description

一种改性聚苯醚树脂及其应用 技术领域
本发明涉及覆铜板技术领域，尤其涉及一种改性聚苯醚树脂及其应用。
背景技术
聚苯醚树脂具有很好的耐热性、介电性能和韧性，在层压板等复合材料中具有很好的应用前途。但是，由于聚苯醚与传统的热固性树脂之间存在极性差异，相容性较差，易于分相，因此聚苯醚的应用存在各种难度。为了增强聚苯醚与热固性树脂之间的相容性，多篇专利中提出了解决方案，但在可行性和成本等方面都有不足。
CN1458963A中提到PPO与三烷基三聚氰酸酯固化物形成IPN结构，其PPO结构中侧链上与苯环链接的为H或可能各自不同的1至3个碳氢化合物群；CN102206415中提到一种氰酸酯、氮氧杂环化合物和聚苯醚，其所用聚苯醚的结构中侧链上为H或甲基。
诸多专利中对侧链的基团一般定义为H或1至3个碳氢化合物群，或不做限定。但是该类聚苯醚树脂与环氧树脂等热固性树脂的相容性较差，常在固化物中存在分相的“海岛”现象，影响树脂基体的均匀性，对电性能、耐热性等造成负面影响。
CN102702680A中提到一种聚苯醚与环氧树脂的组合物，其所用聚苯醚的分子量较小，与环氧树脂的相容性较好，但其Df偏高；CN103102484A中提到了一种可交联的聚苯醚树脂，其结构中侧链上与苯环链接的也是H或1至3个碳氢化合物群；CN105419348A中提到一种端基环氧基改性的聚苯醚树脂，其聚苯醚结构侧链位置是H或1至8个碳氢化合物群，但是未描述其侧链位置碳氢化 合物群的存在意义，而且在常用的聚苯醚树脂的结构中间部分改变其侧链的碳氢化合物群是一件较复杂的工艺。
目前的技术中，一般采用降低聚苯醚的分子量，或在聚苯醚的端基引入反应基团，以改善聚苯醚与热固性树脂的相容性，但对板材的介电性能等造成负面影响，且改善效果不够理想。
发明内容
基于此，本发明的目的之一在于提供一种具有长碳链结构的改性聚苯醚树脂，其不仅可以增加聚苯醚与其他树脂之间的相容性，而且有助于降低层压板材的介电常数和损耗，并且可以提高树脂体系对金属箔的粘结性。
发明人为实现上述目的，进行了反复深入的研究，结果发现：通过采用结构中包含至少一组碳元素大于3的碳氢化合物群的聚苯醚树脂，并将其与环氧树脂、固化剂、固化促进剂及其他可选地物质适当混合而得到的热固性树脂组合物，可达到上述目的。
为了实现上述目的，本发明采用了如下技术方案：
一种改性聚苯醚树脂，所述改性聚苯醚树脂结构中包含至少一组碳元素大于3的碳氢化合物群。
本发明采用结构中包含至少一组碳元素大于3的碳氢化合物群的聚苯醚树脂，不仅可以增加聚苯醚与其他树脂之间的相容性，对树脂体系的分相“海岛”现象有明显的改善，而且有助于降低层压板材的介电常数和损耗，并且可以提高树脂体系对金属箔的粘结性，保持了板材的耐热性能。
根据本发明，所述聚苯醚树脂结构中包含至少一组碳元素大于3的碳氢化合物群，例如可以是一组、两组或多组碳元素大于3的碳氢化合物群，其中关于碳氢化合物群的碳元素数目，例如可以是4、5、6、7、8、9、10、11、12、 13、14、15、16、17、18、19或20。
本发明中，所述聚苯醚树脂结构中优选包含至少一组碳元素大于6的碳氢化合物群，进一步优选包含至少一组碳元素大于9的碳氢化合物群。
本发明采用上述优选地聚苯醚树脂，出乎意料地改善了聚苯醚与环氧树脂、氰酸酯等热固性树脂相容性差的问题，减少或消除了树脂体系的分相“海岛”的粒径，增加了聚苯醚与其他树脂之间的结合力，提高了板材树脂基体的均匀性，并改善了板材的介电性能，提高板材的剥离强度和耐冲击性能。
根据本发明，所述改性聚苯醚树脂是由具有长碳链的酚类化合物与聚苯醚树脂在过氧化物等作用下反应得到的，其中具有长碳链的酚类化合物是指具有长碳链和酚羟基的化合物，其结构式优选如式(I)或(II)所示：
Figure PCTCN2017084317-appb-000001
其中，R1、R2、R3或R4各自独立地为H或CkHj，k为1～20的整数，j为2k-3～2k+1的整数；式(I)中，R1和R2至少有一个为CmHn，m为4～20的整数，例如4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20，n为2m-3～2m+1的整数；式(II)中，R1、R2、R3或R4至少有一个为CmHn，m为4～20的整数，例如4、5、6、7、8、9、10、11、12、13、14、15、16、17、18、19或20，n为2m-3～2m+1的整数。
本发明还提供了一种热固性树脂组合物，其按重量百分含量包含以下组分：
(A)如前所述的改性聚苯醚树脂：5％～45％；
(B)环氧树脂组合物：15％～60％；
(C)固化剂：5％～50％；
(D)固化促进剂：0.01％～3％。
其中(A)、(B)、(C)、(D)各组分的百分含量为不含溶剂的含量。
根据本发明，以(A)、(B)、(C)和(D)的总量计，其中所述改性聚苯醚树脂的重量百分含量为5％～45％，例如5％、6％、8％、10％、12％、15％、18％、20％、22％、25％、28％、30％、35％、38％、40％、42％或45％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，除了含有如前所述的改性聚苯醚树脂外，还可以包含其他种类的低分子量改性聚苯醚树脂，该低分子量聚苯醚树脂的分子量为1000～7000，例如1000、2000、3000、4000、5000、6000或7000，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为1500～4000；同时，本发明还可包含结构中两端为羟基、环氧基或胺基的低分子量改性聚苯醚树脂。
根据本发明，以(A)、(B)、(C)和(D)的总量计，其中所述环氧树脂组合物的重量百分含量为15％～60％，例如15％、16％、18％、20％、22％、25％、28％、30％、35％、40％、42％、45％、50％、52％、55％、58％或60％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述环氧树脂组合物包含双酚A型、双酚F型、双环芴二烯性或联苯型环氧树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为双酚A型和双酚F型环氧树脂、双环芴二烯性和联苯型环氧树脂等。
本发明中的环氧树脂组合物优选包含数均分子量较低的环氧树脂，其数均 分子量优选为200～600，例如200、250、300、350、400、500或600，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值；该部分环氧树脂占所有环氧树脂的重量百分含量为10％～90％，例如10％、20％、30％、40％、50％、60％、70％、80％或90％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值，优选为30％～70％。
优选地，本发明中的环氧树脂组合物还可以包含侧链有碳链结构的环氧树脂以及在甲苯中溶解性较好的环氧树脂。
根据本发明，以(A)、(B)、(C)和(D)的总量计，其中所述固化剂的重量百分含量为5％～50％，例如5％、6％、8％、10％、12％、15％、18％、20％、25％、30％、32％、35％、40％、42％、45％、48％或50％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述固化剂包含胺类固化剂、酸酐类固化剂、咪唑类固化剂、酚醛树脂固化剂、氰酸酯或苯并噁嗪树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为胺类固化剂和酸酐类固化剂、酸酐类固化剂和咪唑类固化剂、氰酸酯和苯并噁嗪树脂等。
根据本发明，以(A)、(B)、(C)和(D)的总量计，其中所述固化促进剂的重量百分含量为0.01％～3％，例如0.01％、0.05％、0.1％、0.5％、0.6％、0.8％、0.9％、1％、1.2％、1.5％、1.8％、2％、2.2％、2.5％、2.8％或3％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述固化促进剂为2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、 三正丁胺、三苯基磷、三氟化硼的络合物或者锌、铜、铁、锡、钴、铝的辛酸、乙酰丙酮、环烷酸、水杨酸或硬脂酸盐中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为2-甲基咪唑和2-苯基咪唑、2-乙基-4-甲基咪唑和三正丁胺、环烷酸和水杨酸等。
根据本发明，所述热固性树脂组合物按重量百分含量还包含(E)填料：5％～45％；即以热固性树脂组合物总量计，填料的重量百分含量为5％～45％，例如5％、6％、8％、10％、12％、15％、18％、20％、25％、30％、32％、35％、40％、42％或45％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述填料可以选自有机填料或无机填料，其中，无机填料可以选自球形硅微粉、熔融硅微粉、氢氧化铝、勃姆石、滑石粉或空心玻璃珠中的任意一种或至少两种的混合物，有机填料可以选自聚四氟乙烯粉末和/或核壳橡胶。
根据本发明，所述热固性树脂组合物按重量百分含量还包含(F)阻燃剂：5％～25％；即以热固性树脂组合物总量计，阻燃剂的重量百分含量为5％～25％，例如5％、6％、8％、10％、12％、13％、14％、15％、18％、20％、22％、24％或25％，以及上述数值之间的具体点值，限于篇幅及出于简明的考虑，本发明不再穷尽列举所述范围包括的具体点值。
本发明中，所述阻燃剂可以选自十溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺、三聚氰胺磷酸盐、三聚氰胺聚磷酸盐、二三聚氰胺焦磷酸盐、三(三溴苯基)三聚氰酸酯、三(2，6-二甲基苯基)磷、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-磷菲-10-氧化物、2，6-二(2，6-二甲基苯基)磷基苯、10-苯基-9，10-二氢-9-氧杂-10-磷菲-10-氧化物或磷腈类化合物中的任意一种或者至少两种的 混合物，其中典型但非限制性的混合物为：十溴二苯醚和十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺和三聚氰胺磷酸盐、10-苯基-9，10-二氢-9-氧杂-10-磷菲-10-氧化物和磷腈类化合物等。
本发明所述的“包含”，意指其除所述组份外，还可以包括其他组份，这些其他组份赋予所述热固性树脂组合物不同的特性。除此之外，本发明所述的“包含”，还可以替换为封闭式的“为”或“由……组成”。
例如，所述热固性树脂组合物还可以含有各种添加剂或助剂，作为具体例，可以举出硅烷偶联剂、填料分散剂、消泡剂、抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些添加剂或助剂可以单独使用，也可以两种或者两种以上混合使用。
本发明的热固性树脂组合物的制备方法为本领域的常规技术手段，其具体方法为：先将固形物放入，然后加入液态溶剂，搅拌至固形物完全溶解后，再加入液态树脂和促进剂，继续搅拌均匀即可。
作为本发明中的溶剂，没有特别的限定，作为具体例，可以列举出甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇甲醚、卡必醇、丁基卡必醇等醚类，丙酮、丁酮、甲基乙基甲酮、环己酮等酮类；甲苯、二甲苯等芳香烃类；醋酸乙酯、乙氧基乙基乙酸酯等酯类；N，N-二甲基甲酰胺、N，N-二甲基乙酰胺等含氮类溶剂。以上溶剂可单独使用，也可两种或两种以上混合使用。优选丙酮、丁酮、甲基乙基甲酮、环己酮等酮类。所述溶剂的添加量由本领域技术人员根据自己经验来选择，使得树脂胶液达到适合使用的粘度即可。
本发明还提供了一种树脂胶液，其是将如前所述的热固性树脂组合物溶解或分散在溶剂中得到。
本发明还提供了一种半固化片，其是将基料浸润如前所述的树脂胶液后， 干燥得到。
本发明的预浸料包括增强材料及含浸干燥后附着在增强材料上的如前所述的热固性树脂组合物，所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无特别限定，处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的混合物。将增强材料通过含浸上述的热固性树脂组合物，在100～250℃条件下，烘烤1～15分钟得到所述预浸料。
本发明的印刷电路板用覆铜箔层压板包括通过加热和加压，使两片或两片以上的粘结片粘合在一起而制成的层压板、粘合在层压板的一面或两面以上的铜箔；所述的覆铜箔层压板是使用上述的粘结片8片和两片一盎司(35μm厚)的铜箔叠合在一起，通过热压机中层压，从而压制成双面覆铜箔层压板；所述的覆铜箔层压需满足以下要求：1、层压的升温速率通常在料温80～160℃时的升温速度应控制在1.0～3.0℃/min；2、层压的压力设置，外层料温在80～100℃时施加满压，满压压力为300psi左右；3、固化时，控制料温在185℃，并保温90min；所覆盖的金属箔除铜箔外，还可以是镍箔、铝箔及SUS箔等，其材质不限。
与现有技术相比，本发明至少具有以下有益效果：
本发明提供的改性聚苯醚树脂具有至少一组碳元素大于3的碳氢化合物群，其不仅可以增加聚苯醚与其他树脂之间的相容性，对树脂体系的分相“海岛”现象有明显的改善，其最大分相“海岛”尺寸的结果显示无分相或＜5μm；而且 有助于降低层压板材的介电常数和损耗，其中Dk值在3.6～3.9范围内，Df值在0.006～0.008之间，剥离强度可达到1.0以上，并且可以提高树脂体系对金属箔的粘结性，保持了板材的耐热性能，而且制造工艺简单，易于实施。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
下文中如无特别说明，其份代表重量份，其％代表“重量％”。
制备例1～7和对比制备例1
将100份聚苯醚粉末、200份甲苯和特定份数的酚类化合物(种类和份数见表1)加入带有搅拌、加热和回流装置的反应釜中，搅拌并加热至95℃，保温搅拌使其完全溶解。将特定份数的过氧化物分为十份，依次投入反应釜中，保温8h，得到低分子化改性的聚苯醚树脂的甲苯溶液。将上述甲苯溶液在旋转蒸发仪中浓缩，然后在甲醇中滴加，过滤得到沉淀物，在鼓风烘箱内，以100℃烘干沉淀物，即得到低分子化改性的聚苯醚树脂。以甲苯为流动相，测定树脂的数均分子量(Mn)，结果如表1所示。
表1
Figure PCTCN2017084317-appb-000002
Figure PCTCN2017084317-appb-000003
实施例1～9和对比例1～3
将制备例所得的改性聚苯醚、环氧树脂和氰酸酯树脂在甲苯中充分溶解(Dicy在DMF中充分溶解)，然后与2乙基-4甲基咪唑和异辛酸锌等促进剂(种类和份数见表2)混合均匀，得到聚苯醚树脂组合物的甲苯溶液。
将NE型玻璃纤维布(日东纺株式会社，NEA2116)浸渍该树脂组合物，并于155℃烘干2～10min，除去溶剂，使挥发份小于1％，树脂的凝胶时间为150s～200s，得到树脂含量在55％左右的半固化片。
在四张重叠的半固化片的两面各覆一张HOz的反转铜箔，在200℃的温度和3.0MPa的压力下热压90min，得到双面覆铜箔层压板。
表2
Figure PCTCN2017084317-appb-000004
Figure PCTCN2017084317-appb-000005
Figure PCTCN2017084317-appb-000006
实施例10～14和对比例4～6
将制备例所得的改性聚苯醚，环氧树脂，氰酸酯树脂在甲苯中充分溶解，然后与2乙基-4甲基咪唑和异辛酸锌等促进剂混合均匀，然后加入填料和阻燃剂(种类和份数见表3)，并通过搅拌和高速剪切等手段分散均匀，得到聚苯醚树脂组合物的甲苯溶液。
将NE型玻璃纤维布(日东纺株式会社，NEA2116)浸渍该树脂组合物，并于155℃烘干2～10min，除去溶剂，使挥发份小于1％，树脂的凝胶时间为150s～200s，得到树脂含量在55％左右的半固化片。
在四张重叠的半固化片的两面各覆一张HOz的反转铜箔，在200℃的温度和3.0MPa的压力下热压90min，得到双面覆铜箔层压板。
表3
Figure PCTCN2017084317-appb-000007
Figure PCTCN2017084317-appb-000008
以上特性的测试方法如下：
1)挥发性：将制备好的半固化片在155℃下烘烤10min，测量半固化片的质量损失，损失超过2％说明有挥发；
2)凝胶时间：采用凝胶测试仪，测试温度171℃；
3)介电常数(Dk)和介电损耗因数(Df)：使用谐振腔法(SPDR)测定；
4)玻璃化转变温度(Tg)：使用动态热机械分析(DMA)测试，升温速率为20℃/min；
5)热失重温度(Td)：使用热失重分析仪(TGA)测试，升温速率为10℃/min，取5％失重时的温度；
6)剥离强度(PS)：指在室温下将每毫米铜箔剥离覆铜板所需的拉力；
7)阻燃：按照UL94“50W(20mm)垂直燃烧试验：V-0、V-1和V-2”测试方法测试，认定V-0为阻燃；
8)落锤冲击：使用漆膜冲击器测试，取冲击后出现裂纹的面积；
9)最大分相“海岛”尺寸：采用扫描电子显微镜(SEM)观测板材横截面，取最大分相区域“海岛”的直径；
10)低分子化后的聚苯醚数均分子量Mn：使用GPC测试制备例所得改性聚苯醚的甲苯溶液，取GPC谱图主峰位置的数均分子量(Mn)，测试流动相为甲苯。
通过上述结果可以看出，实施例1～9和10～14通过采用本发明的改性聚苯醚树脂所得树脂组合物，其最大分相“海岛”尺寸的结果显示无分相或5μm以下，从而说明本发明的改性聚苯醚树脂与其它树脂之间具有较好的相容性；而对比例1～3和4～6中采用未改性的低分子量聚苯醚SA120或低分子量聚苯醚SA90所得树脂组合物，其最大分相“海岛”尺寸的结果显示至少达到10μm，从而说明该未改性的聚苯醚树脂与其它树脂之间的相容性较差。
另外，通过实施例1～9和10～14也可以看出，其得到的板材的Dk值在3.6～3.9，Df值在0.006～0.008之间，明显低于对比例1～3和4～6中的Dk值3.9～4.1和Df值0.009～0.012，表明其介电性能要优于对比例1～3和4～6；另外，实施例1～9所得板材中的剥离强度可达到1.0以上，明显高于对比例1～3的剥离强度(0.5～0.8)，实施例10～14所得板材中的剥离强度再0.8～1.1之间，明显高于对比例4～6中的剥离强度(0.3～0.6)，由此也可以说明，本发明通过采用经改性的聚苯醚树脂所得树脂组合物，其不仅与其它树脂体系增强了相容性，而且有效改善了板材的介电性能，提高了板材的剥离强度和耐冲击性能，还保持了板材的Tg、Td等耐热性能。
通过以上所述，本领域的普通技术人员可以根据本发明的技术方案和技术构思作出其他种类的相应改变和变形，但所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (10)

  1. 一种改性聚苯醚树脂，其特征在于，所述改性聚苯醚树脂结构中包含至少一组碳元素大于3的碳氢化合物群。
  2. 如权利要求1所述的改性聚苯醚树脂，其特征在于，所述改性聚苯醚树脂结构中包含至少一组碳元素大于6的碳氢化合物群，优选包含至少一组碳元素大于9的碳氢化合物群。
  3. 如权利要求1或2所述的改性聚苯醚树脂，其特征在于，所述改性聚苯醚树脂由具有长碳链的酚类化合物与聚苯醚树脂在过氧化物的作用下反应得到；
    优选地，所述具有长碳链的酚类化合物是指具有长碳链和酚羟基的化合物，其结构式如式(I)或(II)所示：
    Figure PCTCN2017084317-appb-100001
    其中，R1、R2、R3或R4各自独立地为H或CkHj，k为1～20的整数，j为2k-3～2k+1的整数；
    式(I)中，R1和R2至少有一个为CmHn，m为4～20的整数，n为2m-3～2m+1的整数；式(II)中，R1、R2、R3或R4至少有一个为CmHn，m为4～20的整数，n为2m-3～2m+1的整数。
  4. 一种热固性树脂组合物，其特征在于，按重量百分含量包含以下组分：
    (A)权利要求1-3之一所述的改性聚苯醚树脂：5％～45％；
    (B)环氧树脂组合物：15％～60％；
    (C)固化剂：5％～50％；
    (D)固化促进剂：0.01％～3％。
  5. 如权利要求4所述的热固性树脂组合物，其特征在于，所述环氧树脂组合物包含双酚A型、双酚F型、双环芴二烯性或联苯型环氧树脂中的任意一种或至少两种的混合物；
    优选地，所述环氧树脂组合物包含数均分子量为200～600的环氧树脂，其占所述环氧树脂组合物总重量的10％～90％，优选30％～70％；
    优选地，所述环氧树脂组合物包含侧链有碳链结构的环氧树脂；
    优选地，所述固化剂包含胺类固化剂、酸酐类固化剂、咪唑类固化剂、酚醛树脂固化剂、氰酸酯或苯并噁嗪树脂中的任意一种或至少两种的混合物；
    优选地，所述固化促进剂为2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、三正丁胺、三苯基磷、三氟化硼的络合物或者锌、铜、铁、锡、钴、铝的辛酸、乙酰丙酮、环烷酸、水杨酸或硬脂酸盐中的任意一种或至少两种的混合物；
    优选地，所述热固性树脂组合物还包含分子量为1000～7000的低分子量改性聚苯醚树脂，优选分子量为1500～4000的低分子量改性聚苯醚树脂，进一步优选结构中两端为羟基、环氧基或胺基的低分子量改性聚苯醚树脂。
  6. 如权利要求4或5所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物按重量百分含量还包含(E)填料：5％～45％；
    优选地，所述填料选自有机填料或无机填料；
    优选地，所述无机填料为球形硅微粉、熔融硅微粉、氢氧化铝、勃姆石、滑石粉或空心玻璃珠中的任意一种或至少两种的混合物；
    优选地，所述有机填料为聚四氟乙烯粉末和/或核壳橡胶；
    优选地，所述热固性树脂组合物按重量百分含量还包含(F)阻燃剂：5％～25％；
    优选地，所述阻燃剂为十溴二苯醚、十溴二苯乙烷、乙撑双四溴邻苯二甲酰亚胺、三聚氰胺磷酸盐、三聚氰胺聚磷酸盐、二三聚氰胺焦磷酸盐、三(三溴苯基)三聚氰酸酯、三(2，6-二甲基苯基)磷、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-磷菲-10-氧化物、2，6-二(2，6-二甲基苯基)磷基苯、10-苯基-9，10-二氢-9-氧杂-10-磷菲-10-氧化物或磷腈类化合物中的任意一种或至少两种的混合物；
    优选地，所述热固性树脂组合物还包含(G)助剂；
    优选地，所述助剂为硅烷偶联剂、填料分散剂或消泡剂中的任意一种或至少两种的混合物。
  7. 一种树脂胶液，其特征在于，其是将权利要求4-6之一所述的热固性树脂组合物溶解或分散在溶剂中得到。
  8. 一种半固化片，其特征在于，其是将基料浸润权利要求7所述的树脂胶液后，干燥得到。
  9. 一种层压板，其特征在于，包含至少一张如权利要求8所述的半固化片，进行层压成型制备得到。
  10. 一种印制电路板，其特征在于，包含至少一张如权利要求9所述的层压板。
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