WO2018120563A1 - 一种无卤环氧树脂组合物以及使用它的预浸料和层压板 - Google Patents

一种无卤环氧树脂组合物以及使用它的预浸料和层压板 Download PDF

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WO2018120563A1
WO2018120563A1 PCT/CN2017/082801 CN2017082801W WO2018120563A1 WO 2018120563 A1 WO2018120563 A1 WO 2018120563A1 CN 2017082801 W CN2017082801 W CN 2017082801W WO 2018120563 A1 WO2018120563 A1 WO 2018120563A1
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Prior art keywords
epoxy resin
halogen
weight
parts
phosphorus
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PCT/CN2017/082801
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English (en)
French (fr)
Inventor
何烈相
曾宪平
徐浩晟
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广东生益科技股份有限公司
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Publication of WO2018120563A1 publication Critical patent/WO2018120563A1/zh

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    • 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
    • B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic 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
    • 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
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    • 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
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • 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
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
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    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • B32B2250/20—All layers being fibrous or filamentary
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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
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    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
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    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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 invention belongs to the technical field of copper clad laminates, and particularly relates to a halogen-free epoxy resin composition and a prepreg, a laminate and a printed circuit board using the same.
  • halogen flame retardants For a long time, laminates for printed circuit boards usually use halogen flame retardants to achieve flame retardant purposes. However, when halogen flame retardants are burned, not only smoke is large, smell is unpleasant, and highly corrosive hydrogen halide gas is generated. . In other literatures, in recent years, halogen-containing flame retardants produce carcinogens such as dioxins and dibenzofurans during pyrolysis and combustion at high temperatures. Therefore, with the EU Directive on Waste Electrical and Electronic Equipment and The Directive on the Restriction of the Use of Hazardous Substances in Electrical and Electronic Equipment was officially implemented on July 1, 2006. The development of laminates for halogen-free flame-retardant printed circuit has become the focus of the industry.
  • CN105392817A, CN104204031A, CN103965588A, etc. all have synthetic or even resin compositions containing phosphorus active esters, but they are unable to maintain a high heat resistance, low dielectric constant, low dielectric loss factor and high resistance to moist heat.
  • halogen-free epoxy resin composition In view of the problems of the prior art, it is an object of the present invention to provide a halogen-free epoxy resin composition. And prepregs and laminates using it.
  • the laminate produced using the halogen-free epoxy resin composition has advantages of high heat resistance, low dielectric constant, low dielectric loss factor, high heat and humidity resistance, and low water absorption, and can realize halogen-free flame retardancy.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, found that the above object can be attained by a composition obtained by appropriately mixing an epoxy resin and a phosphorus-containing active ester resin having a specific structure, and other optional components.
  • the present invention provides a phosphorus-containing active ester resin having a structure as shown in the formula (I):
  • a and A 1 are each independently selected from Any of them;
  • P1, q1, m1 and n1 represent repeating units, wherein p1 and q1 are each independently an integer greater than or equal to 1, for example 1, 2, 3, 4, 5 or 6 and above; m1 and n1 represent average degree of polymerization, 0 ⁇ M1 ⁇ 3, for example, m1 may be 0.25, 1, 1.2, 2, 2.5 or 3, m1 may not be 0; 0 ⁇ n1 ⁇ 3, for example, n1 may be 0, 0.25, 0.5, 1, 1.2, 2, 2.6 or 3. ;
  • Z is -CH 2 -, Any of them;
  • R is any one of hydrogen, an aliphatic functional group or an aromatic functional group
  • Y is Or a derivative thereof, or a structure represented by the formula (I n ):
  • Y n and Y n ' are each independently selected from Or a derivative thereof, or a structure represented by the formula (I n+1 ), n is a positive integer of ⁇ 4, and p2, q2, m2 and n2 represent a repeating unit, wherein p2 and q2 are each independently an integer of 1 or more For example, 1, 2, 3, 4, 5 or 6 and above; m2, n2 represent the average degree of polymerization, 0 ⁇ m2 ⁇ 3, for example, m2 may be 0.25, 1, 1.2, 2, 2.5 or 3, and m2 may not be 0. ; 0 ⁇ n1 ⁇ 3, for example, n1 may be 0, 0.25, 0.5, 1, 1.2, 2, 2.6 or 3; B is an integer of 0 to 2, such as 1 or 2.
  • the phosphorus-containing active ester resin having the structure of the formula (a) has a number average molecular weight of between 500 and 5,000, and may be, for example, 500, 600, 700, 800, 900, 1200, 1500, 2100, 2800, 3000, 3500, 4100, 4500 or 5000, and the specific point values between the above values, which are 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.
  • the formula (I n ) is not a specific formula, and when n is 4, the group Y 4 and Y are present in the formula (II 4 ).
  • the invention adopts a phosphorus-containing active ester resin, which has better crosslinkability than ordinary phosphorus-containing phenolic resin, and can improve crosslink density, reactivity with epoxy resin and glass transition temperature. And because of its structure An ester group which has no secondary hydroxyl group after reacting with an epoxy, and has the advantages of high heat resistance, low dielectric constant, low dielectric loss factor, high heat and humidity resistance, low water absorption and halogen-free flame retardancy. .
  • the phosphorus-containing active ester resin has the following structure:
  • a and A 1 are each independently selected from Any of them;
  • P1, q1, m1 and n1 represent repeating units, wherein p1 and q1 are each independently an integer greater than or equal to 1, m1 and n1 represent average polymerization degrees, and m1 and n1 are arbitrary numbers between 0.25 and 3;
  • Z is R is hydrogen; X is
  • Y 1, Y 2 and Y 3 are each independently selected from Or the structure shown by the formula (I n ):
  • Y n and Y n ' are each independently selected from Or a structure represented by the formula (I n+1 ), n is a positive integer ⁇ 4, and p2, q2, m2, and n2 represent repeating units, wherein p2 and q2 are each independently an integer greater than or equal to 1, m2, n2 represent The average degree of polymerization, m2 and n2 are arbitrary numbers between 0.25 and 3; B is an integer of 0 to 2;
  • the phosphorus-containing active ester resin having the structure of the formula (a) has a number average molecular weight of from 500 to 5,000.
  • the present invention also provides a halogen-free epoxy resin composition
  • a halogen-free epoxy resin composition comprising the following components:
  • the phosphorus-containing active ester resin as described above, it does not generate secondary hydroxyl groups after reacting with the halogen-free epoxy resin, and can also have high heat resistance, low dielectric constant, and low dielectric loss. Factors, high moisture and heat resistance, low water absorption and the advantages of halogen-free flame retardant.
  • the addition of the halogen-free epoxy resin can significantly improve the heat resistance and curing crosslink density of the cured product, and can be specifically selected from the group consisting of a biphenolic epoxy resin, a DCPD type epoxy resin, and an alkylene group.
  • Phenolic epoxy resin bisphenol A novolac epoxy resin, bisphenol F epoxy resin, bisphenol Z ring Oxygen resin, bisphenol AP type epoxy resin, bisphenol TMC type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, phenol novolak type epoxy resin, cresol novolac type Epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac Type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol copolycondensation novolak type epoxy resin, naphthol-cresol copolycondensation novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic Any one or a mixture of at least two of a resin type epoxy resin, a biphenyl modified novolak type epoxy resin or an imide modified epoxy resin,
  • the halogen-free epoxy resin is any one of a biphenyl novolak epoxy resin, a DCPD type novolac epoxy resin or a bisphenol A type novolac epoxy resin, or a mixture of at least two.
  • the halogen-free epoxy resin is a biphenol novolac epoxy resin or/and a DCPD type novolac epoxy resin, which has both good heat resistance and dielectric properties.
  • the parts by weight of the halogen-free epoxy resin and the phosphorus-containing active ester resin have an epoxy equivalent ratio of the halogen-free epoxy resin to the ester group equivalent ratio of the phosphorus-containing active ester resin: 1: (0.9) ⁇ 1.1)
  • the ratio of the two is 1: (0.95 ⁇ 1.05), such as 1:0.9, 1:0.95, 1:1, 1:1.05 or 1:1.1, preferably 1: (0.95 ⁇ 1.05), and
  • the specific point values between the above values are 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.
  • the halogen-free epoxy resin composition may further include a crosslinking agent, and the crosslinking agent can effectively enhance the crosslinking curing effect of the epoxy resin.
  • the crosslinking agent is added in an amount of 11 to 37 parts by weight, for example, 11 parts by weight, based on 100 parts by weight of the halogen-free epoxy resin, the phosphorus-containing active ester resin, and the crosslinking agent.
  • Parts by weight 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight or 37 parts by weight, and between the above values
  • the specific point values limited to the length and for the sake of brevity, are not exhaustively enumerated to the specific point values included in the range, preferably 24 to 37 parts by weight.
  • the crosslinking agent is any one of an active ester, an acid anhydride compound or a phenol resin or a mixture of at least two, wherein a typical but non-limiting crosslinking agent is an active ester and an acid anhydride compound, an acid anhydride compound or Phenolic Resin.
  • the active ester is an active ester crosslinking agent having a functional group ester group
  • the acid anhydride compound may be a compound such as styrene maleic anhydride
  • the phenolic resin may be a novolac resin, a biphenol novolac resin, an alkylphenol phenol resin, A hydroxyl group-containing phenol resin such as DCPD phenol resin.
  • the crosslinking agent is an active ester active/and anhydride compound having better dielectric properties relative to the phenolic resin.
  • the crosslinking agent is an active ester having a structure in which a rigid structure such as a benzene ring, a naphthalene ring or a cyclopentadiene imparts high heat resistance to the active ester due to a specific structure of the active ester.
  • a rigid structure such as a benzene ring, a naphthalene ring or a cyclopentadiene
  • X is phenyl or naphthyl
  • j is 0 or 1
  • k is 0 or 1
  • n represents a repeating unit of 0.25 to 1.25, such as 0.25, 0.5, 0.75, 1, 1.05 or 1.25, and a specific point 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 halogen-free epoxy resin composition may further comprise a cyanate ester or a prepolymer thereof.
  • the utility model can improve the glass transition temperature of the composition, and simultaneously achieves N-P synergistic flame retardation with the phosphorus-containing active ester resin, thereby improving flame retardant efficiency.
  • the cyanate ester may be a cyanate ester compound containing at least two cyanooxy groups in a molecule such as a bisphenol A type cyanate ester or a prepolymer thereof, which can better enhance the vitrification of the composition. Change the temperature.
  • the cyanate ester or a prepolymer thereof is added in an amount of 10 to 20 parts by weight, based on 100 parts by weight of the sum of the halogen-free epoxy resin, the phosphorus-containing active ester resin, and the crosslinking agent added, for example, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight or 20 parts by weight, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention is no longer exhaustive The specific point values included in the scope.
  • the halogen-free epoxy resin composition further includes a curing accelerator which cures the resin and accelerates the curing speed of the resin.
  • the curing agent accelerator is added in an amount of 0.05 to 1 part by weight, such as 0.05, based on 100 parts by weight of the sum of the halogen-free epoxy resin, the phosphorus-containing active ester resin, and the crosslinking agent.
  • Parts by weight 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight, 0.5 parts by weight, 0.55 parts by weight, 0.60 parts by weight, 0.65 parts by weight , 0.7 parts by weight, 0.75 parts by weight, 0.8 parts by weight, 0.85 parts by weight, 0.9 parts by weight or 1 part by weight, and the specific point values between the above values, limited to the length and for the sake of brevity, the present invention is no longer exhaustive The range includes specific point values.
  • the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl 4-ethylimidazole or 2-phenylimidazole, zinc isooctanoate or at least two mixture.
  • the present invention may optionally additionally add at least one specific flame retardant compound.
  • the halogen-free epoxy resin composition may further include a flame retardant compound, and the flame retardancy
  • the compound is a flame retardant salt such as a phosphate compound or a nitrogen-containing phosphate compound, but is not limited thereto.
  • the flame retardant compound is added in an amount of 0 to 50 parts by weight, for example, 1 based on 100 parts by weight of the sum of the halogen-free epoxy resin, the phosphorus-containing active ester resin, and the crosslinking agent.
  • Parts by weight 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight, and the specific values between the above values
  • Point values, limited to length and for the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the ranges.
  • the halogen-free epoxy resin composition may further comprise a filler, which is an organic or/and inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering coefficient of thermal expansion (CTE) and reducing water absorption. Rate and increase thermal conductivity, etc.
  • a filler which is an organic or/and inorganic filler, which is mainly used to adjust some physical properties of the composition, such as lowering coefficient of thermal expansion (CTE) and reducing water absorption. Rate and increase thermal conductivity, etc.
  • the filler is added in an amount of from 0 to 100 parts by weight, for example, 0.5 parts by weight, based on 100 parts by weight of the sum of the halogen-free epoxy resin, the phosphorus-containing active ester resin, and the crosslinking agent.
  • the inorganic filler is fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide Any one or a mixture of at least two of barium sulfate, barium titanate, barium titanate, calcium carbonate, calcium silicate, mica or fiberglass powder, wherein a typical but non-limiting mixture is: fused silica And crystalline silica, spherical silica and hollow silica, aluminum hydroxide and aluminum oxide, talc and aluminum nitride, boron nitride and silicon carbide, barium sulfate and barium titanate, barium titanate and Calcium carbonate.
  • the organic filler is selected from the group consisting of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder. Any one or a mixture of at least two, wherein typical but non-limiting mixtures are: polytetrafluoroethylene powder and polyphenylene sulfide, polyethersulfone powder and polytetrafluoroethylene powder, polyphenylene sulfide and polyethersulfone powder , polyphenylene sulfide and polyethersulfone powder.
  • the filler is silica, and the filler has a median particle diameter of 1 to 15 ⁇ m, and preferably the filler has a median particle diameter of 1 to 10 ⁇ m.
  • the halogen-free epoxy resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more kinds.
  • the conventional preparation method of the halogen-free epoxy resin composition of the invention taking a container, first putting the solid component, then adding the liquid solvent, stirring until completely dissolved, adding liquid resin, filler, flame retardant and curing promotion
  • the agent can be stirred evenly, and finally the solvent is used to adjust the liquid solid content to 60% to 80% to prepare a glue.
  • the present invention also provides a prepreg comprising a reinforcing material and a halogen-free epoxy resin composition as described above adhered thereto by impregnation and drying.
  • Exemplary reinforcing materials are nonwoven fabrics and/or other fabrics such as natural fibers, organic synthetic fibers, and inorganic fibers.
  • the prepreg is obtained by heating and drying the impregnated reinforcing material in an oven at 155 to 170 ° C for 5 to 10 minutes by using a woven fabric or an organic fabric such as a glass cloth impregnated reinforcing material.
  • the present invention also provides a laminate comprising at least one prepreg as described above.
  • the present invention also provides a printed circuit board comprising at least one prepreg as described above.
  • the present invention has the following beneficial effects:
  • the phosphorus-containing active ester resin in the present invention can be used as a curing agent for an epoxy resin, and can provide a halogen-free flame retardant property, and has an ester group having no secondary hydroxyl group after reacting with an epoxy compound in its structure.
  • the invention can significantly improve the problems of poor heat and humidity resistance, high dielectric constant and dielectric loss factor of the phosphorus-containing phenolic resin, and the reaction with the epoxy resin is easy and the crosslinking density is large compared with the existing phosphorus-containing active ester resin.
  • the composition has higher glass transition temperature and better heat and humidity resistance, and significantly improves the use of phosphorus-containing phenolic resin and active ester as co-cured epoxy resin, sacrificing part of dielectric constant, dielectric loss factor and water absorption. In addition to the rate and other issues, it is still not possible to significantly improve the Tg of the composition;
  • reaction vessel 260 g of phenol, 200 g of 4,4'-dihydroxybiphenyl, 648 g of an aqueous formaldehyde solution (mass concentration: 37%) and 24 g of sodium hydroxide were charged, and stirring was started, and the temperature was heated to 40 ° C for 3 hours. Then, the temperature was raised to 65 ° C, and after maintaining for 3 hours, 1480 g of n-butanol was added and refluxed for 12 hours. The temperature of the material was lowered to 55-60 ° C, and about 1000 g of n-butanol was distilled off under reduced pressure to obtain an intermediate.
  • the prepregs obtained by using a plurality of sheets are superposed on each other, and a copper foil is respectively pressed on both sides thereof and placed in a heat press to be cured to form the epoxy resin copper clad laminate.
  • the physical property data is shown in Table 1.
  • Example 2 The production process was the same as in Example 1, and the formulation composition and physical property index are shown in Tables 1-2.
  • the table is based on the weight of solid components.
  • NC-3000H Biphenol novolac epoxy resin (trade name of Nippon Chemical Co., Ltd.).
  • DCPD type phenolic epoxy resin (DIC trade name).
  • HPC-8000-65T Active ester curing agent (Japanese DIC trade name).
  • EF-40 styrene maleic anhydride (trade name of Sadoma).
  • CE01PS bisphenol A type cyanate (Yangzhou Tianqi Chemical Trade Name).
  • BYK-W903 filler dispersant (BYK trade name).
  • DMAP curing accelerator, 4-dimethylaminopyridine (Golden Chemical Co., trade name).
  • Zinc isooctanoate curing accelerator (Alfa Aesar trade name).
  • Tg Glass transition temperature
  • PCT and PCT water absorption rate After etching the copper foil indicated by the copper clad laminate, the substrate is evaluated: The plate was placed in a pressure cooker and treated at 120 ° C and 105 KPa for 6 hours: then immersed in a tin furnace at 288 ° C. When the substrate was layered, the corresponding time was recorded: when the substrate was in the tin furnace for more than 5 minutes, it did not appear. The evaluation can be ended when bubbles or delamination.
  • Comparative Example 3 has a PCT layered blasting plate using a conventional phosphorus-containing phenolic resin, and has poor dielectric constant, dielectric loss factor, and heat and humidity resistance and vitrification. The transition temperature was low; Comparative Example 2 used the existing active ester resin, although it improved the dielectric properties and the heat and humidity resistance, but it could not provide a halogen-free flame retardant, and the Tg was very low; and Comparative Example 1, Comparative Example 2 was used.
  • Comparative Example 6 uses epoxy resin without filler + phosphorus. Phenolic resin + active ester resin, although providing halogen-free flame retardant, but no Balance in the overall performance, and its Tg, Dk / Df, PCT and PCT water absorption characteristics with respect to the same without filler Example 14 is worse.
  • Examples 1 to 14 employ a halogen-free epoxy resin and a phosphorus-containing active ester resin, or a composition thereof blended with other optional components, and have high heat resistance, low dielectric constant, and low dielectric.
  • the advantages of loss factor, high moisture heat resistance and low water absorption rate, and halogen-free flame retardancy can be achieved; from Examples 6 and 8, the composition composed of B1 has a higher Tg and better overall performance.
  • the halogen-free circuit substrate of the present invention has high heat resistance, low dielectric constant, low dielectric loss factor, high heat and humidity resistance, low water absorption, and halogen-free resistance as compared with a general laminate. Burning.

Abstract

本发明提供了一种无卤环氧树脂组合物以及使用它的预浸料和层压板。该无卤环氧树脂组合物包括：(A)无卤环氧树脂和(B)含磷活性酯树脂。使用这种无卤环氧树脂组合物制成的预浸料和层压板，具有高耐热性、低介电常数、低介电损耗因子、高耐湿热性和低吸水率的优点，且能实现无卤阻燃。

Description

一种无卤环氧树脂组合物以及使用它的预浸料和层压板 技术领域
本发明属于覆铜板技术领域，具体涉及一种无卤环氧树脂组合物以及使用它的预浸料、层压板和印制电路板。
背景技术
一直以来，印制电路用层压板通常采用卤素阻燃剂达到阻燃目的，但卤素阻燃剂在燃烧时，不但发烟量大，气味难闻，而且会产生腐蚀性很强的卤化氢气体。另有文献报道，近年来在含卤素的阻燃剂在高温裂解和燃烧时会产生二噁英、二苯并呋喃等致癌物质，因此，随着欧盟《关于报废电气电子设备指令》和《关于在电气电子设备中限制使用有害物质指令》于2006年7月1日正式实施，无卤阻燃型印制电路用层压板的开发成为了业界的重点。
另一方面，随着电子元器件朝着，小型轻量薄型化、高性能化、多功能化的方向发展，随之带来的是高频、高速的信号传输。除此之外，高多层PCB板因CCL的耐湿热性和吸水性差而导致的分层爆板问题，引起了极大的关注。
CN105392817A、CN104204031A、CN103965588A等都有合成，甚至运用含磷活性酯的树脂组合物，但其均无法保持高耐热性、低介电常数、低介电损耗因子和高耐湿热性的平衡。
为此，如何在保持组合物具有高耐热性的同时，兼具好的介电常数、介电损耗因子和高耐湿热性以及低吸水率，又能实现无卤阻燃是本领域亟待解决的技术问题。
发明内容
针对已有技术的问题，本发明的目的在于提供一种无卤环氧树脂组合物以 及使用它的预浸料和层压板。使用该无卤环氧树脂组合物制造的层压板具有高耐热性、低介电常数、低介电损耗因子、高耐湿热性和低吸水率的优点，且能实现无卤阻燃。
本发明人为实现上述目的进行了反复深入的研究，结果发现：通过将环氧树脂和特殊结构的含磷活性酯树脂，及其他可选地组分适当混合得到的组合物，可达到上述目的。
为达此目的，本发明采用了如下技术方案：
首先，本发明提供了一种含磷活性酯树脂，其具有如式(I)所示的结构：
Figure PCTCN2017082801-appb-000001
其中，A和A1各自独立地选自
Figure PCTCN2017082801-appb-000002
中的任意一种；
p1、q1、m1和n1表示重复单元，其中p1、q1各自独立地为大于等于1的整数，例如1、2、3、4、5或6及以上；m1、n1表示平均聚合度，0＜m1≤3，例如m1可以是0.25、1、1.2、2、2.5或3，m1不可以为0；0≤n1≤3，例如n1可以是0、0.25、0.5、1、1.2、2、2.6或3；
Z为-CH2-、
Figure PCTCN2017082801-appb-000003
中的任意一种；
R为氢、脂肪族官能基或芳香族官能基中的任意一种；
X为
Figure PCTCN2017082801-appb-000004
Y为
Figure PCTCN2017082801-appb-000005
或其衍生物，或式(In)所示的结构：
Figure PCTCN2017082801-appb-000006
式(In)中，Yn和Yn’各自独立地选自
Figure PCTCN2017082801-appb-000007
或其衍生物，或式(In+1)所示的结构，n为≥4的正整数，p2、q2、m2和n2表示重复单元，其中p2、q2各自独立地为大于等于1的整数，例如1、2、3、4、5或6及以上；m2、n2表示平均聚合度，0＜m2≤3，例如m2可以是0.25、1、1.2、2、2.5或3，m2不可以为0；0≤n1≤3，例如n1可以是0、0.25、0.5、 1、1.2、2、2.6或3；B为0～2的整数，例如1或2。
所述具有式(a)结构的含磷活性酯树脂的数均分子量为500～5000之间，例如可以是500、600、700、800、900、1200、1500、2100、2800、3000、3500、4100、4500或5000，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。
本发明所述具有式(a)结构的含磷活性酯树脂中，式(In)并不是一个特定的通式，当n为4时，式(II4)中具有支链Y4和Y4’，且Y4和Y4’分别各自独立地为
Figure PCTCN2017082801-appb-000008
或其衍生物，或式(I5)所示的结构；此时的式(I5)中具有支链Y5和Y5’，且Y5和Y5’分别各自独立地为为
Figure PCTCN2017082801-appb-000009
或其衍生物，或式(I6)所示的结构；……(以此若干循环)，式(In)中具有支链Yn和Yn’，且Yn和Yn’分别各自独立地为
Figure PCTCN2017082801-appb-000010
或其衍生物，或式(In)所示的结构；但是，对于具有式(a)结构的含磷活性酯树脂式(In)的结构不能无限循环，当通过循环达到分子量为500～5000时，可以采用氢原子进行封端。
本发明采用含磷活性酯树脂，相较于普通含磷酚醛树脂有较佳的交联性，可提高交联密度、与环氧树脂的反应性及玻璃转化温度。又因为其结构中具有 与环氧反应后没有二次羟基的酯基，使其兼具有高耐热性、低介电常数、低介电损耗因子、高耐湿热性和低吸水率和实现无卤阻燃的优点。
优选地，所述含磷活性酯树脂具有如下结构：
Figure PCTCN2017082801-appb-000011
其中，A和A1各自独立地选自
Figure PCTCN2017082801-appb-000012
中的任意一种；
p1、q1、m1和n1表示重复单元，其中p1、q1各自独立地为大于等于1的整数，m1、n1表示平均聚合度，m1、n1为0.25～3之间的任意数；
Z为
Figure PCTCN2017082801-appb-000013
R为氢；X为
Figure PCTCN2017082801-appb-000014
Y1、Y2和Y3各自独立地选自
Figure PCTCN2017082801-appb-000015
或式(In)所示的结构：
Figure PCTCN2017082801-appb-000016
式(In)中，Yn和Yn’各自独立地选自
Figure PCTCN2017082801-appb-000017
或式(In+1)所示的结构，n为≥4的正整数，p2、q2、m2和n2表示重复单元，其中p2、q2各自独立地为大于等于1的整数，m2、n2表示平均聚合度，m2、n2为0.25～3之间的任意数；B为0～2的整数；
所述具有式(a)结构的含磷活性酯树脂的数均分子量为500～5000之间。
本发明还提供了一种无卤环氧树脂组合物，其包括如下组分：
(A)无卤环氧树脂；
(B)如前所述的含磷活性酯树脂。
本发明中通过采用如前所述的含磷活性酯树脂，其与无卤环氧树脂反应后不产生二次羟基，还能使其具有高耐热性、低介电常数、低介电损耗因子、高耐湿热性、低吸水率和实现无卤阻燃的优点。
根据本发明，所述无卤环氧树脂的加入可以明显改善固化物的耐热性和固化交联密度，其具体可以选自联苯酚醛环氧树脂、DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂、双酚A型酚醛环氧树脂、双酚F型环氧树脂、双酚Z型环 氧树脂、双酚AP型环氧树脂、双酚TMC型环氧树脂、含联苯型环氧树脂、四甲基联苯型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、三苯基甲烷型环氧树脂、四苯基乙烷型环氧树脂、双环戊二烯-苯酚加成反应型环氧树脂、苯酚芳烷基型环氧树脂、萘酚酚醛清漆型环氧树脂、萘酚芳烷基型环氧树脂、萘酚-苯酚共缩聚酚醛清漆型环氧树脂、萘酚-甲酚共缩聚酚醛清漆型环氧树脂、芳香族烃甲醛树脂改性酚醛树脂型环氧树脂、联苯改性酚醛清漆型环氧树脂或酰亚胺改性环氧树脂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：联苯酚醛环氧树脂和DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂和双酚A型酚醛环氧树脂、双酚AP型环氧树脂和双酚TMC型环氧树脂。
优选地，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD型酚醛环氧树脂或双酚A型酚醛环氧树脂中的任意一种或者至少两种的混合物。
更优选地，所述无卤环氧树脂为联苯酚醛环氧树脂或/和DCPD型酚醛环氧树脂，其兼具好的耐热性和介电性能。
根据本发明，优选地，所述无卤环氧树脂和含磷活性酯树脂的重量份，按无卤环氧树脂的环氧当量与含磷活性酯树脂的酯基当量比为1∶(0.9～1.1)进行计算，优选两者比例为1∶(0.95～1.05)，例如1∶0.9、1∶0.95、1∶1、1∶1.05或1∶1.1，优选1∶(0.95～1.05)，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，所述无卤环氧树脂组合物还可以包括交联剂，交联剂可有效提升和环氧树脂的交联固化作用。
根据本发明，以无卤环氧树脂、含磷活性酯树脂和交联剂的添加量为100重量份计，所述交联剂的添加量为11～37重量份，例如11重量份、12重量份、 15重量份、18重量份、20重量份、22重量份、25重量份、28重量份、30重量份、32重量份、33重量份、34重量份或37重量份，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24～37重量份。
根据本发明，所述交联剂为活性酯、酸酐化合物或酚醛树脂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交联剂为活性酯和酸酐化合物、酸酐化合物或酚醛树脂。
优选地，所述活性酯为具有官能团酯基的活性酯交联剂，酸酐化合物可以为苯乙烯马来酸酐等化合物，酚醛树脂可为线性酚醛树脂、联苯酚酚醛树脂、烷基酚酚醛树脂、DCPD酚醛树脂等含羟基的酚醛树脂。
进一步优选地，所述交联剂为活性酯活/和酸酐化合物，其相对酚醛树脂，具有更好的介电性能。
更优选地，所述交联剂为具有如下结构的活性酯，由于该活性酯的特殊结构，其中的苯环、萘环、环戊二烯等刚性结构赋予该活性酯高的耐热性，同时由于其结构的规整性及与环氧树脂反应过程中无二次羟基产生，赋予其良好的电性能和低的吸水性。
Figure PCTCN2017082801-appb-000018
X为苯基或者萘基，j为0或1，k为0或1，n表示重复单元为0.25～1.25，例如0.25、0.5、0.75、1、1.05或1.25，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，所述无卤环氧树脂组合物还可进一步包括氰酸酯或其预聚物， 其可提升组合物的玻璃化转变温度，同时与含磷活性酯树脂实现N-P协同阻燃，提高阻燃效率。
优选地，所述氰酸酯可以为双酚A型氰酸酯等分子中含有至少2个氰氧基的氰酸酯化合物或及其预聚物，其可更好地提升组合物的玻璃化转变温度。
以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为100重量份计，所述氰酸酯或其预聚物的添加量为10～20重量份，例如10重量份、12重量份、14重量份、16重量份、18重量份或20重量份，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。
优选地，所述无卤环氧树脂组合物还包括固化促进剂，其使树脂固化并加快树脂固化速度。
优选地，以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为100重量份计，所述固化剂促进剂的添加量为0.05～1重量份，例如0.05重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量份、0.60重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份或1重量份，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。
优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑、异辛酸锌中的任意一种或者至少两种的混合物。
为进一步提高无卤环氧树脂组合物的难燃特性，于较佳的情形中，本发明尚可选择性添加至少一种特定的阻燃性化合物。
优选地，所述无卤环氧树脂组合物还可包括阻燃性化合物，所述阻燃性化 合物为阻燃性盐类，如磷酸盐化合物或含氮磷酸盐化合物，但并不仅限于此。
优选地，以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为100重量份计，所述阻燃性化合物的添加量为0～50重量份，例如1重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份或50重量份，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。
优选地，所述无卤环氧树脂组合物还可以包含填料，所述填料为有机或/和无机填料，其主要用来调整组合物的一些物性效果，如降低热膨胀系数(CTE)、降低吸水率和提高热导率等。
优选地，以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为100重量份计，所述填料的添加量为0～100重量份，例如0.5重量份、1重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重量份、95重量份或100重量份，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0～50重量份。
优选地，所述无机填料为熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母或玻璃纤维粉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：熔融二氧化硅和结晶型二氧化硅、球型二氧化硅和空心二氧化硅、氢氧化铝和氧化铝、滑石粉和氮化铝、氮化硼和碳化硅、硫酸钡和钛酸钡、钛酸锶和碳酸钙。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的 任意一种或者至少两种的混合物，其中典型但非限制性混合物为：聚四氟乙烯粉末和聚苯硫醚、聚醚砜粉末和聚四氟乙烯粉末、聚苯硫醚和聚醚砜粉末、聚聚苯硫醚和聚醚砜粉末。
优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选填料的粒径中度值为1～10μm。
本发明所述的“包括”，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无卤环氧树脂组合物不同的特性。除此之外，本发明所述的“包括”，还可以替换为封闭式的“为”或“由......组成”。
例如，所述无卤环氧树脂组合物还可以含有各种添加剂，作为具体例，可以举出抗氧剂、热稳定剂、抗静电剂、紫外线吸收剂、颜料、着色剂或润滑剂等。这些各种添加剂可以单独使用，也可以两种或者两种以上混合使用。
本发明的无卤环氧树脂组合物的常规制作方法：取一容器，先将固体组分放入，然后加入液体溶剂，搅拌直至完全溶解后，加入液体树脂、填料、阻燃剂和固化促进剂，继续搅拌均匀即可，最后用溶剂调整液体固含量至60％～80％而制成胶液。
本发明还提供了一种预浸料，其包括增强材料及通过含浸干燥后附着其上的如上所述的无卤环氧树脂组合物。
示例性的增强材料如无纺织物或/和其他织物，例如天然纤维、有机合成纤维以及无机纤维。
使用该胶液含浸增强材料如玻璃布等织物或有机织物，将含浸好的增强材料在155～170℃的烘箱中加热干燥5～10分钟即可得到预浸料。
本发明还提供了一种层压板，其包括至少一张如上所述的预浸料。
本发明还提供了一种印制电路板，其包括至少一张如上所述的预浸料。
与现有技术相比，本发明具有如下有益效果：
(1)在本发明中的含磷活性酯树脂，可作为环氧树脂的固化剂，又能提供无卤阻燃特性，且因为其结构中具有与环氧反应后没有二次羟基的酯基，能明显改善含磷酚醛树脂耐湿热性差，介电常数、介电损耗因子过高等问题，且相对于现有的含磷活性酯树脂，其与环氧树脂反应容易，交联密度大，使组合物具有更高的玻璃化转变温度和更好的耐湿热性，明显改善了使用含磷酚醛树脂和活性酯作为共固化环氧树脂，牺牲了部分的介电常数、介电损耗因子和吸水率等问题外，依然无法明显改善组合物Tg过低的情况；
(2)使用该无卤环氧树脂组合物制作的预浸料、层压板和覆金属箔层压板，具有高高耐热性、低介电常数、低介电损耗因子、高耐湿热性和低吸水率的优点，且能实现无卤阻燃。
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。
根据上述所制成的无卤环氧树脂组合物覆金属箔层压板，测试其玻璃化转变温度、介电常数、介电损耗因子、PCT和PCT吸水率、燃烧性，如下述实施例加于详细说明与描述，其中有机树脂的质量份按有机固形物质量份计。
制备例1：含磷活性酯树脂B1制备
在安装有温度计、滴液漏斗、冷凝管、分馏管、搅拌器的烧瓶中加入1mol含磷酚醛DHP-60H(江苏雅克科技股份有限公司商品名)和816g甲基异丁基酮(MIBK)，将体系内减压氮气置换，使其溶解。接着，投入0.9mol对苯二甲酰氯，反应2h，体系内温度控制在60℃以下；然后，向体系中加入1.2mol苯酚，继续反应1h；通氮气条件下，缓慢滴加189g的20％氢氧化钠水溶液；在该条件下继续搅拌1小时。反应结束后，静止分液除去水层。在反应物溶解的MIBK 相中投入水，搅拌混合，静止分液，除去水层。重复上述操作直至水层的PH达到7.0左右。然后通过倾析器脱去水分，接着减压蒸馏脱去MIBK，得到活性酯树脂B1。
制备例2：含磷活性酯树脂B2制备
在反应釜中投260g苯酚、200g 4，4′-二羟基联苯、648克甲醛水溶液(质量浓度为37％)和24g氢氧化钠，开启搅拌，将温度加热至40℃，保温3小时。然后升温至65℃，保温3小时后，加入1480g正丁醇，回流12小时。将料温降至55-60℃，并减压蒸馏除去1000g左右的正丁醇，得到中间体。
往中间体中加入1080g DOPO(9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物)，在2小时内将料温升从80℃逐步升温至190℃，并在120℃时向体系施加减压以保证正丁醇及时排出体系。在180℃下保温1小时，然后将料温降至135℃，加入900g左右的丙二醇甲醚，继续搅拌0.5小时，放料，得到磷系固化剂A2。
在安装有温度计、滴液漏斗、冷凝管、分馏管、搅拌器的烧瓶中加入1mol A2和816g甲基异丁基酮(MIBK)，将体系内减压氮气置换，使其溶解。接着，投入0.9mol对苯二甲酰氯，反应2h，体系内温度控制在60℃以下；然后，向体系中加入1.2mol苯酚，继续反应1h；通氮气条件下，缓慢滴加189g的20％氢氧化钠水溶液；在该条件下继续搅拌1小时。反应结束后，静止分液除去水层。在反应物溶解的MIBK相中投入水，搅拌混合，静止分液，除去水层。重复上述操作直至水层的PH达到7.0左右。然后通过倾析器脱去水分，接着减压蒸馏脱去MIBK，得到活性酯树脂B2。
实施例1
取一容器，加入100重量份的NC-3000H和28重量份EF-40加入适量的MEK，搅拌溶解后，加入55重量份制备例1中的含磷活性酯树脂和79重量份 的FB-3Y和0.79重量份的BYK-W903，搅拌，加入适量的固化促进剂DMAP，继续搅拌均匀，最后用溶剂调整液体固含量至60％～70％而制成胶液。用玻璃纤维布浸渍上述胶液，即成胶液。用玻璃纤维布浸渍上述胶液，并控制至适当厚度，然后烘干除去溶剂得到预浸料。使用数张所制得的预浸料相互叠合，在其两侧分别压覆一张铜箔，放进热压机中固化制成所述的环氧树脂覆铜板层压板。物性数据如表1所示。
实施例2～14：
制作工艺和实施例1相同，配方组成及其物性指标如表1～2所示。
比较例1～6：
制作工艺与实施例1相同，配方组成及其物性指标如表3所示。
表1
Figure PCTCN2017082801-appb-000019
表2
Figure PCTCN2017082801-appb-000020
表3
Figure PCTCN2017082801-appb-000021
Figure PCTCN2017082801-appb-000022
注：表中皆以固体组分重量份计。
表1～3中列举的材料具体如下：
BI：制备例1的含磷活性酯树脂。
B2：制备例2的含磷活性酯树脂。
92741：含磷酚醛树脂(Dow商品名)。
NC-3000H：联苯酚醛环氧树脂(日本化药商品名)。
7200-3H：DCPD型酚醛环氧树脂(DIC商品名)。
627：双酚A型酚醛环氧树脂(美国Hexion商品名)。
HPC-8000-65T：活性酯固化剂(日本DIC商品名)。
EF-40：苯乙烯马来酸酐(沙多玛商品名)。
2812：线性酚醛树脂(韩国Momentive商品名)。
CE01PS：双酚A型氰酸酯(扬州天启化学商品名)。
525：二氧化硅填料(矽比科商品名)。
BYK-W903：填料分散剂(BYK商品名)。
DMAP：固化促进剂，4-二甲氨基吡啶(广荣化学商品名)。
异辛酸锌：固化促进剂(阿法埃莎商品名)。
以上特性的测试方法如下：
(1)玻璃化转变温度(Tg)：根据差示扫描量热法(DSC)，按照IPC-TM-6502.4.25所规定的DSC方法进行测定。
(2)介电常数和介电损耗因子：按照IPC-TM-650 2.5.5.9所规定的方法进行测试，测试频率为10GHz。
(3)PCT及PCT吸水率：将覆铜板表明的铜箔蚀刻后，评价基板：将基 板放置压力锅中，在120℃、105KPa条件下，处理6个小时：后浸渍于288℃的锡炉中，当基材分层时，记录相应时间：当基板在锡炉中超过5min还没出现气泡或分层时即可结束评价。
(4)燃烧性：依照UL94法规定。
物性分析：
从表1～3的物性数据可知，比较例1～6中，比较例3采用现有的含磷酚醛树脂存在PCT分层爆板，介电常数、介电损耗因子和耐湿热性差且玻璃化转变温度低；比较例2采用现有的活性酯树脂，虽然改善了介电性能和耐湿热性问题，但其无法提供无卤阻燃，且Tg非常低；而比较例1，采用比较例2和3的树脂组合物组合，虽然提供了无卤阻燃，但其无法在综合性能上实现平衡，且其Tg、Dk/Df、PCT特性和PCT吸水率相对于实施例11更差，比较例4和比较例5与实施例11～13比较可知，当比较例4和5无卤环氧树脂与含磷活性酯的重量份不按照环氧树脂当量与含磷活性酯的酯基当量范围进行计算时，会导致板材固化不足，其Tg、Dk/Df、PCT吸水率相对实施例11～13较差，且出现PCT分层爆板，比较例6采用不含填料的环氧树脂+含磷酚醛树脂+活性酯树脂，虽然提供了无卤阻燃，但其无法在综合性能上实现平衡，且其Tg、Dk/Df、PCT特性和PCT吸水率相对于同样不含填料的实施例14更差。
另外，实施例1～14采用无卤环氧树脂和含磷活性酯树脂，或其与其他可选组分共混组成的组合物，兼具高耐热性、低介电常数、低介电损耗因子、高耐湿热性和低吸水率的优点，且能实现无卤阻燃；从实施例6和实施例8可知，由B1组成的组合物的Tg更高，综合性能更好。
如上所述，与一般的层压板相比，本发明的无卤电路基板具有高耐热性、低介电常数、低介电损耗因子、高耐湿热性和低吸水率且能实现无卤阻燃。
以上所述，仅为本发明的较佳实施例，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思做出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的范围。
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种含磷活性酯树脂，其特征在于，所述含磷活性酯树脂具有如式(a)所示的结构：
    Figure PCTCN2017082801-appb-100001
    其中，A和A1各自独立地选自
    Figure PCTCN2017082801-appb-100002
    中的任意一种；
    p1、q1、m1和n1表示重复单元，其中p1、q1各自独立地为大于等于1的整数，m1、n1表示平均聚合度，0＜m1≤3，0≤n1≤3；
    Z为-CH2-、
    Figure PCTCN2017082801-appb-100003
    中的任意一种；
    R为氢、脂肪族官能基或芳香族官能基中的任意一种；
    X为
    Figure PCTCN2017082801-appb-100004
    Y1、Y2和Y3各自独立地选自
    Figure PCTCN2017082801-appb-100005
    或其衍生物，或式(In)所示的结构：
    Figure PCTCN2017082801-appb-100006
    式(In)中，Yn和Yn′各自独立地选自
    Figure PCTCN2017082801-appb-100007
    或其衍生物，或式(In+1)所示的结构，n为≥4的正整数，p2、q2、m2和n2表示重复单元，其中p2、q2各自独立地为大于等于1的整数，m2、n2表示平均聚合度，0＜m2≤3，0≤n2≤3；B为0～2的整数；
    所述具有式(a)结构的含磷活性酯树脂的数均分子量为500～5000之间。
  2. 如权利要求1所述的含磷活性酯树脂，其特征在于，所述含磷活性酯树脂具有如下结构：
    Figure PCTCN2017082801-appb-100008
    其中，A和A1各自独立地选自
    Figure PCTCN2017082801-appb-100009
    中的任意一种；
    p1、q1、m1和n1表示重复单元，其中p1、q1各自独立地为大于等于1的整数，m1、n1表示平均聚合度，m1、n1为0.25～3之间的任意数；
    Z为
    Figure PCTCN2017082801-appb-100010
    R为氢；X为
    Figure PCTCN2017082801-appb-100011
    Y1、Y2和Y3各自独立地选自
    Figure PCTCN2017082801-appb-100012
    或式(In)所示的结构：
    Figure PCTCN2017082801-appb-100013
    式(In)中，Yn和Yn′各自独立地选自
    Figure PCTCN2017082801-appb-100014
    或式(In+1)所示的结构，n为≥4的正整数，p2、q2、m2和n2表示重复单元，其中p2、q2各自独立地为大于等于1的整数，m2、n2表示平均聚合度，m2、n2为0.25～3之间的任意数；B为0～2的整数；
    所述具有式(a)结构的含磷活性酯树脂的数均分子量为500～5000之间。
  3. 一种无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物包括如下组分：
    (A)无卤环氧树脂；
    (B)权利要求1或2所述的含磷活性酯树脂。
  4. 如权利要求3所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD型酚醛环氧树脂、亚烷基酚醛环氧树脂、双酚A型酚醛环氧树脂、双酚F型环氧树脂、双酚Z型环氧树脂、双酚AP型环氧树脂、双酚TMC型环氧树脂、含联苯型环氧树脂、四甲基联苯型环氧树脂、苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、三苯基甲烷型环氧树脂、四苯基乙烷型环氧树脂、双环戊二烯-苯酚加成反应型环氧树脂、苯酚芳烷基型环氧树脂、萘酚酚醛清漆型环氧树脂、萘酚芳烷基型环氧树脂、萘酚-苯酚共缩聚酚醛清漆型环氧树脂、萘酚-甲酚共缩聚酚醛清漆型环氧树脂、芳香族烃甲醛树脂改性酚醛树脂型环氧树脂、联苯改性酚醛清漆型环氧树脂或酰亚胺改性环氧树脂中的任意一种或者至少两种的混合物；
    优选地，所述无卤环氧树脂为联苯酚醛环氧树脂、DCPD型酚醛环氧树脂或双酚A型酚醛环氧树脂中的任意一种或者至少两种的混合物，优选联苯酚醛环氧树脂或/和DCPD型酚醛环氧树脂；
    优选地，所述无卤环氧树脂和含磷活性酯树脂的重量份，按无卤环氧树脂的环氧当量与含磷活性酯树脂的酯基当量比为1∶(0.9～1.1)进行计算，优选两者比例为1∶(0.95～1.05)。
  5. 如权利要求3或4所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包括交联剂；
    优选地，所述交联剂为活性酯、酸酐化合物或酚醛树脂中的任意一种或者至少两种的混合物；
    优选地，所述交联剂为具有如下结构的活性酯：
    Figure PCTCN2017082801-appb-100015
    其中，X为苯基或萘基，j为0或1，k为0或1，n表示重复单元，为0.25～1.25；
    优选地，以无卤环氧树脂、含磷活性酯树脂和交联剂的添加量为100重量份计，所述交联剂的添加量为11～37重量份，优选24～37重量份。
  6. 如权利要求3-5之一所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包括氰酸酯或其预聚物；
    优选地，以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为100重量份计，所述氰酸酯或其预聚物的添加量为10～20重量份；
    优选地，所述无卤环氧树脂组合物还包括固化促进剂；
    优选地，以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为100重量份计，所述固化促进剂的添加量为0.05～1重量份；
    优选地，所述固化促进剂为4-二甲氨基吡啶、2-甲基咪唑、2-甲基4-乙基咪唑或2-苯基咪唑或异辛酸锌中的任意一种或者至少两种的混合物。
  7. 如权利要求3-6之一所述的无卤环氧树脂组合物，其特征在于，所述无卤环氧树脂组合物还包括阻燃性化合物；
    优选地，所述阻燃性化合物为阻燃性盐类，优选磷酸盐化合物或含氮磷酸盐化合物；
    优选地，以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为 100重量份计，所述阻燃性化合物的添加量为0～50重量份；
    优选地，所述无卤环氧树脂组合物还包括填料；
    优选地，所述填料为有机或/和无机填料；
    优选地，以所述无卤环氧树脂、含磷活性酯树脂和交联剂的添加量之和为100重量份计，所述填料的添加量为0～100重量份，优选0～50重量份；
    优选地，所述无机填料为熔融二氧化硅、结晶型二氧化硅、球型二氧化硅、空心二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙或云母或玻璃纤维粉中的任意一种或者至少两种的混合物；
    优选地，所述有机填料为聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物；
    优选地，所述填料为二氧化硅，填料的粒径中度值为1～15μm，优选1～10μm。
  8. 一种预浸料，其包括增强材料及通过含浸干燥后附着其上的如权利要求3-7之一所述的无卤环氧树脂组合物。
  9. 一种层压板，其包括至少一张如权利要求8所述的预浸料。
  10. 一种印制电路板，其包括至少一张如权利要求8所述的预浸料。
PCT/CN2017/082801 2016-12-28 2017-05-03 一种无卤环氧树脂组合物以及使用它的预浸料和层压板 WO2018120563A1 (zh)

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