WO2018227746A1 - Résine polymère et son utilisation dans une carte de circuit imprimé à haute fréquence - Google Patents

Résine polymère et son utilisation dans une carte de circuit imprimé à haute fréquence Download PDF

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WO2018227746A1
WO2018227746A1 PCT/CN2017/097337 CN2017097337W WO2018227746A1 WO 2018227746 A1 WO2018227746 A1 WO 2018227746A1 CN 2017097337 W CN2017097337 W CN 2017097337W WO 2018227746 A1 WO2018227746 A1 WO 2018227746A1
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weight
parts
vinyl
styrene
resin
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PCT/CN2017/097337
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English (en)
Chinese (zh)
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曾宪平
陈广兵
徐浩晟
关迟记
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广东生益科技股份有限公司
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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
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • 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
    • 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
    • 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
    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
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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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • 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
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • 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
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the present invention relates to the field of copper clad laminates, and in particular to a resin composition and its application in high frequency circuit boards, in particular to a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer. Resin and its application in high frequency circuit boards.
  • dielectric constant on performance high-frequency circuits, signal transmission rate and the relationship between the insulating material is a dielectric constant D k: the lower the dielectric constant D k dielectric material, the faster the transmission rate of the signal. Therefore, in order to increase the speed of the signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the frequency of the signal increases, the loss of the signal in the substrate can no longer be ignored.
  • the relationship between the signal loss and the frequency, the dielectric constant D k , and the dielectric loss D f is such that the smaller the substrate dielectric constant D k is, the smaller the dielectric loss D f is, and the smaller the signal loss is. Therefore, the development of a high-frequency circuit substrate having a low dielectric constant D k and a low dielectric loss D f has become a research and development direction common to CCL manufacturers.
  • the prepreg and its substrate can meet the multiple lamination requirements, and it is required to pass multiple lead-free reflow soldering. Requirements such as high heat resistance and low thermal expansion coefficient of the base resin composition are required.
  • An olefin resin such as polybutadiene or styrene-butadiene polymer, which contains a curable cross-linked vinyl double bond, does not contain a polar group, and has a low dielectric constant and dielectric loss, and can be used in a large amount in a high frequency group. Preparation of materials. However, it also exists in the presence of an olefin resin such as polybutadiene or styrene-butadiene polymer in the initiator-initiated polymerization curing strip.
  • the crosslink density of the cured product is low, the glass transition temperature is low, the prepared substrate has a large thermal expansion coefficient, and the polymerization is initiated by using a peroxide radical initiator, which causes the dielectric constant and dielectric loss of the substrate. Raise.
  • the polypara-hydroxystyrene-based resin can synthesize an active group having a specific structure by modifying the group by modifying it with a reactive group phenolic hydroxyl group.
  • a reactive group phenolic hydroxyl group In particular, non-polar vinyl reactive groups.
  • the prepared substrate has high glass transition temperature, low dielectric constant and dielectric loss, small thermal expansion coefficient and good heat resistance, and can be used for the development of high-frequency circuit substrates.
  • CN87100741A discloses a thermosetting poly(p-hydroxystyryl) derivative resin having a vinyl reactive group which is an allyl group, an isobutenyl group, a vinyl group, an acryloyl group or a methacryloyl group.
  • the resin composition is used for preparing prepregs and laminates having a low dielectric constant, good heat resistance, and good flame retardancy.
  • the vinyl structure selected for the resin has the following problems: 1. For the allyl group, since the radical intermediate is conjugated, it does not have the activity of radical curing; 2.
  • the two vinyl reactive groups contain a certain polar carbonyl chemical structure, which leads to a large dielectric constant and dielectric loss of the prepared substrate.
  • isobutenyl and vinyl groups although it does not contain a polar chemical structure, isobutylene
  • the base and the vinyl need to initiate polymerization under the conditions of the initiator, the crosslink density of the cured product is low, the glass transition temperature is low, the coefficient of thermal expansion is high, and the polymerization is initiated by using a peroxide radical initiator, which causes the dielectric constant of the substrate and An increase in dielectric loss.
  • the inventors synthesized a vinyl benzyl ether modified poly(p-hydroxystyrene-styrene) polymer resin which contains an active styrene group and can be self-cured under heating without The initiation of a peroxide free radical initiator is required.
  • the prepared substrate has high glass transition temperature, low dielectric constant and dielectric loss, and small thermal expansion coefficient, and can be applied to preparation of high frequency circuits.
  • the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin has a high crosslink density and high brittleness, which cannot meet the toughness requirements of the copper clad laminate.
  • Benzyl ether modified poly(p-hydroxybenzene) The brittleness of the vinyl-styrene polymer resin cured product is improved.
  • a composition comprising a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin.
  • the substrate prepared by using the resin composition has a low dielectric constant, low dielectric loss, low thermal expansion coefficient and the like, and the substrate has a small area of "ten" shaped drop under the action of falling weight impact load.
  • the toughness of the substrate is good, which can meet the requirements of the toughness of the copper clad laminate.
  • composition comprising a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, comprising:
  • the substrate prepared by using the resin composition not only has low dielectric constant, low dielectric loss, small thermal expansion coefficient and the like, and the substrate has a small area of "ten"-shaped falling marks under the action of falling weight impact load.
  • the toughness of the substrate is good, which can meet the requirements of the toughness of the copper clad laminate.
  • the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin provided by the invention has a chemical structure as shown in the formula (I):
  • R 1 is as shown in formula (II):
  • n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 18 or 20
  • n is 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 18, 20, 25, 30, 35 or 40.
  • the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin wherein the relationship between m and n in the chemical structural formula (I) is:
  • m/(m+n) may be, for example, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75. %, 80%, 85%, 90%, 95% or 100%.
  • the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin has a number average molecular weight of 1,000 to 20,000, and may be, for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000 or 20000, preferably 2000-5000.
  • the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin is a poly(p-hydroxystyryl-styrene) polymer and vinylbenzyl chloride is reacted by the following formula:
  • R 1 is: Both m and n are natural numbers, and m is not zero.
  • the substrate prepared by modifying the poly(p-hydroxystyryl-styrene) polymer resin with the above vinyl benzyl ether has high glass transition temperature, low dielectric constant and dielectric loss, and small thermal expansion coefficient, it exists in the presence of The joint density is high and the brittleness is large, which cannot meet the requirements of the toughness of the copper clad laminate. Therefore, the brittleness of the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin cured product needs to be improved.
  • the present invention adds a vinyl-modified polyphenylene ether resin to a vinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin, which not only has a substrate prepared using the resin composition
  • the comprehensive properties of high transformation temperature, low dielectric constant, low dielectric loss, low thermal expansion coefficient, etc. also make the substrate have a small area of "ten"-shaped falling marks under the impact load of falling weight, and the toughness of the substrate is good. It can meet the requirements of toughness of CCL.
  • the vinyl modified polyphenylene ether resin has the following structure:
  • 1 ⁇ e ⁇ 100 (for example, may be 1, 3, 5, 8, 10, 22, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc.), 1 ⁇ f ⁇ 100 (for example) It can be 1, 3, 5, 8, 10, 22, 31, 40, 52, 61, 70, 80, 92, 95 or 100, etc., 2 ⁇ e + f ⁇ 100 (for example, it can be 2 ⁇ e + f ⁇ 5,10 ⁇ e+f ⁇ 20, 15 ⁇ e+f ⁇ 30, 25 ⁇ e+f ⁇ 40, 30 ⁇ e+f ⁇ 55, 35 ⁇ e+f ⁇ 45, 60 ⁇ e+f ⁇ 75 , 65 ⁇ e + f ⁇ 85, 80 ⁇ e + f ⁇ 98 or 85 ⁇ e + f ⁇ 100, etc.; and M is selected from:
  • N is selected from any one of -O-, -CO-, -SO-, -SC-, -SO 2 - or -C(CH 3 ) 2 - or a combination of at least two;
  • R 8 , R 10 , R 12 , R 14 , R 17 , R 19 , R 21 and R 23 are each independently selected from substituted or unsubstituted C1 to C8 (eg, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) a linear alkyl group, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl group, substituted or unsubstituted phenyl group Any one or a combination of at least two;
  • R 9 , R 11 , R 13 , R 15 , R 18 , R 20 , R 22 and R 24 are each independently selected from a hydrogen atom, a substituted or unsubstituted C1 to C8 (for example, C1, C2, C3, C4, C5). , C6, C7 or C8, etc.) linear alkyl, substituted or unsubstituted C1-C8 (eg C1, C2, C3, C4, C5, C6, C7 or C8, etc.) branched alkyl, substituted or unsubstituted Any one of phenyl groups or a combination of at least two;
  • R 16 is selected from:
  • the vinyl modified polyphenylene ether resin has a number average molecular weight of 500 to 10000 g/mol, for example, 500 g/mol, 800 g/mol, 1000 g/mol, 1100 g/mol, 1500 g/mol, 4000 g/mol, 5600 g. /mol, 8000 g/mol or 10000 g/mol, etc., preferably 800 to 8000 g/mol, further preferably 1000 to 4000 g/mol.
  • the weight of the vinyl-modified polyphenylene ether resin is 50 to 200 parts by weight based on 100 parts by weight of the vinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin.
  • composition containing a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin may further include a flame retardant.
  • the flame retardant is selected from any one or a mixture of at least two of a bromine-based flame retardant, a phosphorus-based flame retardant or a nitrogen-based flame retardant, wherein a typical but non-limiting mixture is: bromine-based flame retardant a mixture of a phosphorus-based flame retardant, a mixture of a phosphorus-based flame retardant and a nitrogen-based flame retardant, and a mixture of a bromine-based flame retardant and a nitrogen-based flame retardant.
  • the bromine-based flame retardant is selected from any one or a mixture of at least two of decabromodiphenyl ether, decabromodiphenylethane, ethylene bistetrabromophthalimide, wherein A typical but non-limiting mixture is a mixture of decabromodiphenyl ether and decabromodiphenylethane, a mixture of decabromodiphenylethane and ethylene bistetrabromophthalimide, decabromodiphenyl. A mixture of ether and ethylene bis-tetrabromophthalimide.
  • the phosphorus-based flame retardant is selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphinophen-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene or 10-phenyl-9,10-dihydro-9-oxa-10- Any one or a mixture of at least two of phosphaphenanthrene-10-oxides, wherein a typical but non-limiting mixture is: tris(2,6-dimethylphenyl)phosphine and 10-(2,5- a mixture of dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-9,10-dihydro- a mixture of 9-oxa-10-phosphaphenanthrene
  • the nitrogen-based flame retardant is selected from any one or a mixture of at least two of melamine, melamine phosphate, strontium phosphate, cesium carbonate or bismuth sulfamate, wherein a typical but non-limiting mixture is: a mixture of melamine and melamine phosphate, a mixture of strontium phosphate and cesium carbonate, a mixture of cesium carbonate and bismuth sulfamate.
  • the weight of the flame retardant is 0, based on 100 parts by weight of the total weight of the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin and the vinyl modified polyphenylene ether resin.
  • ⁇ 40 parts by weight for example, may be 1 part by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight or 40 parts by weight.
  • the weight of the flame retardant is 0 parts by weight, meaning that the resin composition does not contain a flame retardant.
  • composition containing a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin may further include a powder filler.
  • the powder filler is selected from the group consisting of crystalline silica, amorphous silica, spherical silica, fused silica, titanium dioxide, silicon carbide, glass fiber, alumina, aluminum nitride, boron nitride, Any one or a mixture of at least two of barium titanate or barium titanate, wherein a typical but non-limiting mixture is: a mixture of crystalline silica and amorphous silica, spherical silica and molten A mixture of fused silica, a mixture of titanium dioxide and silicon carbide, a mixture of alumina and barium titanate, a mixture of glass fibers, aluminum nitride and barium titanate.
  • the powder filler functions to improve dimensional stability, lower thermal expansion coefficient, lower system cost, and the like.
  • the shape and particle diameter of the powder filler are not limited in the present invention, and the particle diameter generally used is 0.2 to 10 ⁇ m, for example, 0.2 ⁇ m, 0.5 ⁇ m, 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 5 ⁇ m, 8 ⁇ m, 9 ⁇ m or 10 ⁇ m, for example, Spherical silica having a particle diameter of 0.2 to 10 ⁇ m is selected.
  • the weight of the powder filler is 0 to 150 parts by weight, based on 100 parts by weight of the total weight of the polyvinyl benzyl ether-modified poly(p-hydroxystyryl-styrene) polymer resin and the flame retardant, and may be, for example, 1 Parts by weight, 5 parts by weight, 15 parts by weight, 25 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 75 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight 120 parts by weight, 130 parts by weight, 140 parts by weight, 145 parts by weight or 150 parts by weight.
  • the weight of the powder filler is 0 parts by weight, meaning that the resin composition does not contain a powder filler.
  • the preparation method of the resin composition of the present invention can be prepared by a known method of formulating, stirring, and mixing the above-mentioned resin, flame retardant, powder filler, and various additives.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing the composition as described above in a solvent.
  • 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, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group.
  • Butyl ketone, A ketone flux such as cyclohexanone is used in combination.
  • the amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.
  • An emulsifier may be added during the process of dissolving or dispersing the resin composition as described above in a solvent. By dispersing by an emulsifier, the powder filler or the like can be uniformly dispersed in the glue.
  • a third object of the present invention is to provide a prepreg obtained by dipping a glass fiber cloth in a resin glue as described above and drying it.
  • the glass fiber cloth is a reinforcing material, and functions to increase strength, improve dimensional stability, and reduce shrinkage of curing of the thermosetting resin in the composite material.
  • Different types of fiberglass cloth can be used depending on the thickness of the sheet and the like.
  • Exemplary glass fiber cloths are: 7628 fiberglass cloth, 2116 fiberglass cloth.
  • the total weight of the poly(p-hydroxystyryl-styrene) polymer resin, the vinyl modified polyphenylene ether resin, the flame retardant and the powder filler modified with vinyl benzyl ether is 100 parts by weight, and the glass fiber cloth is used.
  • the weight is 50 to 230 parts by weight, and may be, for example, 50 parts by weight, 70 parts by weight, 90 parts by weight, 110 parts by weight, 150 parts by weight, 180 parts by weight, 200 parts by weight, 210 parts by weight, 220 parts by weight or 230 parts by weight. Share.
  • the drying temperature is 80-220 ° C, for example, 80 ° C, 90 ° C, 110 ° C, 150 ° C, 170 ° C, 190 ° C, 200 ° C or 220 ° C; the drying time is 1 ⁇ 30 min, for example, may be 1 min , 3 min, 5 min, 8 min, 13 min, 17 min, 21 min, 24 min, 28 min or 30 min.
  • a fourth object of the present invention is to provide a copper clad laminate comprising at least one prepreg as described above.
  • a fifth object of the present invention is to provide an insulating sheet comprising at least one prepreg as described above.
  • a sixth object of the present invention is to provide a high frequency circuit substrate comprising at least one prepreg as described above.
  • the substrate prepared by using the resin composition of the invention has the advantages of low dielectric constant, low dielectric loss, low thermal expansion coefficient, etc., and the toughness of the substrate is good, and the surface and interior of the substrate are under a small bending force. No cracks are formed, which can meet the requirements of toughness of copper clad laminates.
  • the high frequency circuit substrate provided by the present invention may be prepared by the following steps:
  • At least one prepreg as described above is overlapped, and a copper foil is placed on the upper and lower sides of the overlapping prepreg, and is obtained by lamination molding.
  • the overlap preferably employs an automated stacking operation to make the process operation easier.
  • the laminate molding is preferably vacuum lamination molding, and the vacuum lamination molding can be carried out by a vacuum laminator.
  • the lamination time is 70-120 min, for example, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min or 120 min;
  • the lamination temperature is 180-220 ° C, for example Is 180 ° C, 185 ° C, 190 ° C, 195 ° C, 200 ° C, 205 ° C, 210 ° C, 215 ° C or 220 ° C;
  • the pressure of the lamination is 40 ⁇ 60 kg / cm 2 , for example, may be 40 kg / cm 2 , 45kg / cm 2, 50kg / cm 2, 55kg / cm 2, 58kg / cm 2 or 60kg / cm 2.
  • a typical but non-limiting method for preparing a high frequency circuit substrate of the present invention is as follows:
  • each component is weighed, specifically: the weight of the poly(p-hydroxystyryl-styrene) polymer resin modified with vinyl benzyl ether is 100 parts by weight.
  • the weight of the vinyl modified polyphenylene ether resin is 50 to 200 parts by weight; the poly(p-hydroxystyryl-styrene) polymer resin modified with vinyl benzyl ether and the vinyl modified polyphenylene ether resin
  • the total weight is 100 parts by weight, the weight of the flame retardant is 0-40 parts by weight; the poly(p-hydroxystyryl-styrene) polymer resin modified with vinyl benzyl ether, vinyl modified polyphenylene ether
  • the total weight of the resin and the flame retardant is 100 parts by weight, and the weight of the powder filler is 0 to 150 parts by weight;
  • High frequency as used herein means that the frequency is greater than 100 MHz.
  • the present invention has at least the following beneficial effects:
  • the present invention is applied to a copper clad laminate by modifying a poly(p-hydroxystyryl-styrene) polymer resin with a vinyl benzyl ether, since the chemical structure does not contain a polar group, thereby Ensure that the prepared substrate has excellent low dielectric constant and low dielectric loss performance;
  • the present invention is applied to a copper clad laminate by modifying a poly(p-hydroxystyryl-styrene) polymer resin with a vinyl benzyl ether, which has a high crosslink density and a large amount of benzene.
  • the ring-rigid structure has a high glass transition temperature and a low coefficient of thermal expansion relative to the substrate prepared by the olefin resin;
  • the present invention can improve the brittleness of a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin cured product by using a vinyl modified polyphenylene ether resin as a toughening agent. Under the impact load of the falling weight, the material has a small area of "ten"-shaped falling marks and good toughness of the substrate, which can meet the requirements of the toughness of the copper-clad board.
  • the poly(p-hydroxystyrene-styrene) polymer resin composition modified with vinyl benzyl ether has a high-frequency circuit substrate having high glass transition temperature, low dielectric constant, low dielectric loss, and thermal expansion coefficient. Small, and the substrate has a small area of "ten"-shaped falling marks under the impact load of the falling weight, and the toughness of the substrate is good, which can meet the requirements of the toughness of the copper-clad board, and is very suitable for the circuit for preparing high-frequency electronic equipment. Substrate.
  • Figure 1 is a schematic diagram of a test system for evaluating the toughness of a substrate using a drop hammer impact method
  • Figure 2 is an external view of the drop hammer, wherein Figure 2-1 is a visual view of the drop hammer, and Figure 2-2 is a bottom view of the drop hammer;
  • Figure 3 is the appearance of the drop of 0.50 kg of falling weight and the effect of samples A, B, C, D, E;
  • Figure 4 is a schematic view showing a standard square frame having a side length of 50 ⁇ 0.1 mm placed in the middle of a sample drop;
  • Figure 5 is a selection diagram of the effective area of the drop
  • Figure 6 is a scale view of the area of the drop and the standard frame.
  • test system diagram is shown in Figure 1; the front end of the drop hammer is a 10mm diameter ball head with a drop weight of 0.50kg, 0.75kg and 1.00kg respectively, the appearance of which is shown in Figure 2; under the action of the drop hammer impact load When the weight is 0.50 kg, the appearance of the "ten"-shaped falling marks produced by the substrate is as shown in FIG.
  • the "ten" shape of the falling area analysis method is shown in Fig. 4, Fig. 5 and Fig. 6, in which a standard square frame with a side length of 50 ⁇ 0.1 mm is placed in the middle of the sample drop, see Fig. 4, and photographed. Place the image in the CAD software and zoom in to the white spot that can be finely observed at the edge of the drop.
  • the function of the software use the mouse to select the "ten" pattern of the falling mark and the white point area around it, and obtain the Figure 5, and then select the standard square box area in Figure 4 to obtain Figure 6. Calculate the actual area of the selected area according to the function of the software.
  • Table 1 shows the materials used in the examples and comparative examples.
  • the CST15 containing 1 mol of phenolic hydroxyl group was dissolved in an ethanol solvent, mechanically stirred until completely dissolved, and the temperature was raised to 50 ° C, and nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; and 1.2 mol of vinylbenzyl chloride was added thereto. 8 hours; after the end of the reaction, the product is precipitated from ethanol, dissolved in toluene, washed once or twice with water; precipitated in ethanol, and the precipitated product is dissolved in toluene to obtain a vinyl benzyl ether modified poly(p-hydroxybenzene). Vinyl-styrene) polymer SY-2, ready for use.
  • the CST50 containing 1 mol of phenolic hydroxyl group was dissolved in an ethanol solvent, mechanically stirred until completely dissolved, and the temperature was raised to 50 ° C, and nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; and 1.2 mol of vinylbenzyl chloride was added thereto. 8 hours; after the end of the reaction, the product is precipitated from ethanol, dissolved in toluene, washed once or twice with water; precipitated in ethanol, and the precipitated product is dissolved in toluene to obtain a vinyl benzyl ether modified poly(p-hydroxybenzene). Vinyl-styrene) polymer SY-3, ready for use.
  • the CST70 containing 1 mol of phenolic hydroxyl group is dissolved in an ethanol solvent, mechanically stirred until completely dissolved, and the temperature is raised to 50 ° C, nitrogen gas was introduced for 30 min; 1.2 mol of sodium methoxide was added for 1 hour; 1.2 mol of vinylbenzyl chloride was added for 8 hours; after the reaction, the product was precipitated from ethanol, dissolved in toluene, washed once or 2 times. Then, it was precipitated by dropping into ethanol, and the precipitated product was dissolved in toluene to obtain a vinylbenzyl ether-modified poly(p-hydroxystyryl-styrene) polymer SY-4, which was used.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • a vinylbenzyl ether-modified poly(p-hydroxystyryl-styrene) polymer SY-1 100 parts by weight of a vinylbenzyl ether-modified poly(p-hydroxystyryl-styrene) polymer SY-1 was dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • the overall performance of the substrate is shown in Table 2.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • Example 1 has a small area of "ten"-shaped falling marks
  • Comparative Example 1 is compared with that of Comparative Example 1.
  • the area of the "ten"-shaped drop of the substrate is much larger, which indicates that Example 1 modified the poly(p-hydroxystyryl-styrene) polymer and vinyl-modified polyphenylene ether resin by using vinyl benzyl ether. Combination of vinyl benzyl alone
  • the ether-modified poly(p-hydroxystyryl-styrene) polymer has good toughness of the prepared substrate, and the substrate has a small area of "ten"-shaped falling marks under the action of falling weight impact load. Can meet the toughness requirements of copper clad laminates. Comparing Example 5 with Comparative Example 2, the same results were obtained.
  • the present invention is prepared by blending a poly(p-hydroxystyryl-styrene) polymer modified with a vinyl benzyl ether with a vinyl modified polyphenylene ether resin, and a vinyl modified polyphenylene ether resin as
  • the toughening agent can improve the brittleness of the cured product of the vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer resin, and the prepared substrate is produced under the action of falling weight impact load The shape of the drop is small and the toughness of the substrate is good, which can meet the requirements of the substrate for toughness.
  • the high-frequency circuit substrate prepared in Example 1 had a high glass transition temperature
  • the substrate prepared in Comparative Example 3 had a low glass transition temperature due to MT- 2 uncured polymerization results.
  • SY-1 is self-curing
  • MT-2 is not self-curing and must be polymerized under peroxide free radical initiator conditions.
  • a peroxide radical initiator is used, as shown in Comparative Example 4, an increase in dielectric constant and dielectric loss is caused.
  • the high-frequency circuit substrate prepared in Example 1 had a high glass transition temperature, a low coefficient of thermal expansion, a low dielectric constant, and a dielectric loss, and was prepared in Comparative Example 5.
  • the substrate has a high coefficient of thermal expansion and a peroxide radical initiator is used, resulting in an increase in substrate dielectric constant and dielectric loss.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the fine powder 525 was dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the micropowder SC-2300SVJ is dissolved in a toluene solvent and adjusted to a suitable viscosity.
  • the 2116 prepreg was prepared by infiltrating the resin glue with 2116 glass fiber cloth, controlling the single weight by the clamp shaft, drying in an oven, and removing the toluene solvent.
  • the fine powder 525 is dissolved in a toluene solvent and adjusted to a suitable viscosity; the resin glue is impregnated with a 2116 glass fiber cloth, controlled by a pinch shaft, and dried in an oven to remove the toluene solvent to obtain a 2116 prepreg; Four sheets of 2116 prepreg were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm 2 , and a curing temperature of 200 ° C to obtain a high-frequency circuit substrate.
  • Table 3 The overall performance of the substrate is shown in Table 3.
  • the present invention utilizes a combination of a vinyl benzyl ether modified poly(p-hydroxystyryl-styrene) polymer and a vinyl modified polyphenylene ether resin to provide a prepared substrate having High glass flower transition temperature, low dielectric constant, low dielectric loss, low thermal expansion coefficient and other comprehensive properties, and the toughness of the substrate is good. Under the action of the falling weight impact load, the "ten"-shaped falling mark area is small. Meet the requirements of toughness of CCL.

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Abstract

La présente invention concerne une composition de résine polymère de poly(p-hydroxystyryl-styrène) modifiée par un éther vinylbenzylique, comprenant : (1) une résine polymère de poly(p-hydroxystyryl-styrène) modifiée par un éther vinylbenzylique ; et (2) une résine d'éther polyphénylique modifiée par un vinyle. La présente invention concerne en outre un préimprégné comprenant la composition de résine et son utilisation dans une carte de circuit imprimé à haute fréquence. Un substrat préparé par le biais de la composition de résine présente non seulement des propriétés globales telles qu'une température de transition vitreuse élevée, une faible constante diélectrique, une faible perte diélectrique et un faible coefficient de dilatation thermique, mais présente également une petite zone de trace de chute en forme de « 十 » produite sous l'action d'une charge d'impact de mouton à chute libre, et une bonne ténacité, et peut ainsi satisfaire aux exigences de ténacité des plaques revêtues de cuivre.
PCT/CN2017/097337 2017-06-13 2017-08-14 Résine polymère et son utilisation dans une carte de circuit imprimé à haute fréquence WO2018227746A1 (fr)

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US4784917A (en) * 1985-04-23 1988-11-15 Hitachi, Ltd. Thermosetting resin composition and laminate and process for the production thereof
JPS62161846A (ja) * 1986-01-10 1987-07-17 Hitachi Ltd 熱硬化性樹脂組成物
CN87100741A (zh) * 1986-02-19 1987-12-16 株式会社日立制作所 热固性树脂及使用该树脂制备的半固化片和层压材料
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