WO2015172687A1 - 一种热固性树脂组合物及其用途 - Google Patents

一种热固性树脂组合物及其用途 Download PDF

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WO2015172687A1
WO2015172687A1 PCT/CN2015/078591 CN2015078591W WO2015172687A1 WO 2015172687 A1 WO2015172687 A1 WO 2015172687A1 CN 2015078591 W CN2015078591 W CN 2015078591W WO 2015172687 A1 WO2015172687 A1 WO 2015172687A1
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mass
tert
parts
bis
peroxide
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PCT/CN2015/078591
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English (en)
French (fr)
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罗成
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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
    • 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
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/128—Unsaturated polyimide precursors the unsaturated precursors containing heterocyclic moieties in the main chain
    • 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
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • 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
    • B32B2363/00—Epoxy resins
    • 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
    • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
    • B32B2379/08—Polyimides

Definitions

  • the present invention relates to a thermosetting resin composition and use thereof, and in particular to a thermosetting resin composition, a resin glue liquid using the resin composition, a prepreg, a laminate, and a printed wiring board.
  • BMI resin has good solubility, toughness and processability after being modified by DABPA, but it requires high temperature and long time and more stringent post-treatment conditions in the curing process to meet its high performance requirements. as follows:
  • an initiator of an organic peroxide having a one-hour half-life temperature of greater than 140 ° C is used to initiate polymerization of the bismaleimide and the polyolefin to obtain an insulated power cable.
  • CN 03134502.6 Preparation of bismaleimide, DABPA, epoxy resin, epoxy acrylate and reactive diluent with an organic peroxide initiator BPO or DCP with a one-hour half-life temperature of 80-140 ° C as initiator High temperature resistant composite.
  • CN 101215358 and CN 101215405 are exemplified by an azo initiator having a reaction temperature of 60 to 90 ° C or an organic peroxide initiator of 100 to 130 ° C or a combination thereof.
  • a cold-resistant nitrile rubber composition is prepared by initiating a nitrile rubber and a co-crosslinking agent thereof with an organic peroxide initiator having a one-hour half-life temperature of 130 to 140 °C.
  • CN 101678643 an organic peroxide having a one-hour half-life of 100 to 150 ° C as an initiator, and a hydrogenated nitrile rubber, a bismaleimide, a polyfunctional unsaturated compound, an anti-aging agent, etc., to obtain a binder .
  • CN 101550248 The organic peroxide DCP is used as an initiator to knead the olefin copolymer and zinc stearate, filler, carbon black and a small amount of BMI to obtain a halogen-free flame-retardant polyolefin elastomer.
  • CN 102167825A One or several organic peroxides TBPB/TAPB/DCP having an hour and a half life of 120-135 ° C as an initiator, added to the prepolymer of DABPA/DDS/BMI at 50-100 ° C and The phase transfer catalyst is mixed with an epoxy to prepare a resin composition for preparing a carbon fiber composite rod.
  • Organic hydrogen peroxide is used as a high temperature initiator component in the complex initiator of the system, but the initiation temperature of organic hydrogen peroxide is still slightly lower than that of the BMI/DABPA resin system, and the initiation time is shorter; Organic hydrogen peroxide itself has a low boiling point and is easily volatilized at high temperatures, especially in the CCL manufacturing process, which requires vacuum lamination and solidification, so that organic hydrogen peroxide can easily escape from the system, thereby failing to improve the system.
  • the effect of curing the crosslink density does not contribute significantly to the improvement of the heat resistance and thermal expansion coefficient of CCL.
  • An object of the present invention is to provide a thermosetting resin composition, and a prepreg and a laminate for printed circuit board using the same.
  • the printed circuit board laminate produced using the resin composition has an excellent impact Strength, bending strength and low CTE.
  • thermosetting resin composition comprising, by mass parts:
  • the compounded free radical initiator contains at least one organic peroxide radical initiator having a one-hour half-life temperature of 110 to 150 ° C and at least one carbon-based radical initiator; organic peroxide free radicals
  • the mass ratio of the initiator to the carbon radical free radical agent is from 1 : 1 to 1 : 9.
  • the invention combines the free radical initiator, according to the principle of DABPA modified BMI (bismaleimide) resin polymerization, combined with the production characteristics of the laminate, that is, the resin composition is impregnated on the reinforcing material such as fiberglass cloth. Then it is dried to obtain a prepreg. In the baking process, the temperature is 130 to 155 ° C, which is the temperature range in which the organic peroxide radical initiator acts.
  • DABPA modified BMI bismaleimide
  • the organic peroxide free radical initiator ie, low temperature initiator
  • the carbon-based free radical initiator ie, high temperature initiator
  • the temperature of the D-A addition reaction occurs at about 220 °C. This temperature far exceeds the working range of the organic peroxide and far exceeds the boiling point of the organic peroxide, in which the organic peroxide does not function as a free radical initiator.
  • the amount of the low temperature initiator should not be too large to prevent a large amount of gas from being released during the prepolymerization reaction, thereby causing a large amount of pores in the prepreg, and avoiding excessive prepolymerization, resulting in no fluidity of the bonding sheet when the pressure plate is solidified.
  • the working temperature region of the carbon-based free radical initiator is in this interval, which can initiate the radical polymerization, which can initiate the subsequent DA addition reaction, and the carbon-carbon double bond in the excess BMI during low-temperature baking. Self-polymerization. Because at low temperatures Some of the reactions have already occurred in part, resulting in preliminary prepolymerization of the carbon-carbon double bonds.
  • the amount of the high temperature initiator is not large, and the curing thereof is a long process, and the gas is not generated sharply, resulting in a large amount of bubbles in the copper clad laminate.
  • the content of the at least one bismaleimide compound of the component (B) is 24 to 80 parts by mass, for example, 25 parts by mass, 27 parts by mass, 29 parts by mass, 31 parts by mass, 35 parts by mass, 37% by mass. 39 parts by mass, 41 parts by mass, 43 parts by mass, 45 parts by mass, 47 parts by mass, 49 parts by mass, 51 parts by mass, 53 parts by mass, 55 parts by mass, 57 parts by mass, 59 parts by mass, 61 parts by mass, 63 parts by mass, 65 parts by mass, 67 parts by mass, 69 parts by mass, 71 parts by mass, 73 parts by mass, 75 parts by mass, 77 parts by mass or 79 parts by mass, preferably 28 to 76 parts by mass, more preferably 32 to 72 parts by mass .
  • Different amounts of the component (B) bismaleimide compound may result in different modified bismaleimide prepolymers, and the content of the component (B) bismaleimide compound is 24-80.
  • the use of a compounded initiator can reduce Z-CTE and improve impact strength and bending strength.
  • the diallyl bisphenol compound is a diallyl diphenol compound selected from the group consisting of diallyl bisphenol A, diallyl bisphenol F or diallyl bisphenol S Any one or a mixture of at least two.
  • the mixture is, for example, a mixture of diallyl bisphenol A and diallyl bisphenol F, a mixture of diallyl bisphenol S and diallyl bisphenol A, diallyl bisphenol F and dienes A mixture of propyl bisphenol S, a mixture of diallyl bisphenol A, diallyl bisphenol F and diallyl bisphenol S.
  • the bismaleimide compound is a compound having two maleimide groups in a molecular structure selected from the group consisting of diphenylmethane bismaleimide and diphenyl ether bismaleimide. Or a mixture of any one or a mixture of at least two of diphenyl sulfone bismaleimide or the like.
  • the mixture is, for example, a mixture of diphenylmethane bismaleimide and diphenylether bismaleimide, a mixture of diphenylsulfone bismaleimide and diphenylmethane bismaleimide, diphenyl a mixture of ether bismaleimide and diphenyl sulfone bismaleimide, A mixture of diphenylmethane bismaleimide, diphenyl ether bismaleimide and diphenyl sulfone bismaleimide.
  • the content of the component (C) complex radical initiator is 0.5 to 5 parts by mass, for example, 0.7 parts by mass, 0.9 parts by mass, 1.1 parts by mass, 1.3 parts by mass, 1.5 parts by mass, 1.7 parts by mass, and 1.9 mass.
  • the initiator can be fully priming, avoiding too much initiator to make the radical reaction too fast, resulting in no fluidity of the resin during the bonding process, and can not be pressed into qualified
  • the plate also avoids the residual small molecules remaining in the system after the initiator reaction, so that the Td (5% loss) and heat resistance of the CCL are lowered.
  • the mass ratio of the carbon-based radical initiator to the organic peroxide radical initiator is 1:1 to 1:9, for example, 1:8.5, 1:8, 1:7.5, 1:7, 1:6.5:, 1:6, 1:5.5, 1:5, 1:4.5, 1:4, 1:3.5, 1:3, 1:2.5, 1:2 or 1:1.5, preferably 1:2 to 1:8, further preferably 1:3 to 1:7, more preferably 1:4 to 1:5, most It is preferably 1:4.5 to 1:5.
  • the organic peroxide free radical initiator is selected from the group consisting of t-butyl peroxyacetate, t-butyl peroxy maleate, tert-butyl peroxy 3,5,5-trimethylhexanoate, 1, 1-di(tert-butylperoxy)cyclohexane, 2,2-di(tert-butylperoxy)butane, 1,1-bis(tert-amylperoxy)cycloalkane, 1,1-double (tert-amylperoxy)-3,3,5-trimethylcyclohexane, tert-amyl 2-ethylhexylcarbonate, t-amyl peroxyacetate, 3,5,5 trimethyl peroxide Tert-butyl hexanoate, di-tert-amyl peroxide, tert-butyl peroxybenzoate, t-amyl peroxybenzoate, tert-butyl 2-ethylhexyl
  • the mixture is, for example, a mixture of tert-butyl peroxyacetate and t-butyl peroxymaleate, tert-butyl peroxy 3,5,5-trimethylhexanoate and 1,1-di(tert-butylperoxide) a mixture of cyclohexane, 2,2-di(tert-butylperoxy)butane, 1,1-bis(tert-amylperoxy)cycloalkane and 1,1-bis(tert-amylperoxy) a mixture of -3,3,5-trimethylcyclohexane, tert-amyl 2-ethylhexylcarbonate, t-amyl peroxyacetate and tert-butyl peroxy 3,5,5-trimethylhexanoate a mixture of di-tert-amyl peroxide, tert-butyl peroxybenzoate, t-amyl peroxybenzoate and tert-butyl 2-e
  • the organic peroxide free radical initiator is preferably t-amyl peroxyacetate, tert-butyl peroxy 3,5,5-trimethylhexanoate, di-tert-amyl peroxide, t-butyl peroxybenzoate, Oxidized tert-amyl benzoate, tert-butyl 2-ethylhexylcarbonate, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 3,3-bis(tert-pentyl) Base peroxy) ethyl butyrate, 3,3-bis(t-amylperoxy)butyrate ethyl ester, 3,3-bis(t-amylperoxy)butyrate ethyl ester, 3,3-double (uncle Butyl peroxy)ethyl butyrate, dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, di-ter
  • the carbon-based free radical initiator has the following structure:
  • R 1 and R 3 are the same, and R 1 and R 3 are simultaneously selected from phenyl, substituted or unsubstituted C 1 -C 4 linear alkyl or branched alkyl or Any one of the groups wherein R 5 is a substituted or unsubstituted C1-C4 linear alkyl group or a branched alkyl group;
  • R 2 and R 4 are the same, and R 2 and R 4 are simultaneously selected from -CN, -OH or a substituted or unsubstituted C1 to C4 linear alkyl group or a branched alkyl group;
  • X and Y are independently selected from H, Br, Cl, phenyl, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C2-C4 linear alkenyl or branched Alkenyl or any one of OR 6 , R 6 is a substituted or unsubstituted C1-C4 linear or branched alkyl group or a substituted or unsubstituted C2-C4 linear olefin Base or branched alkenyl group.
  • the carbon-based free radical initiator is selected from the group consisting of 2,3-dimethyl-2,3-diphenylbutane, 2,3-dimethyl Base-2,3-bis(4'-methylphenyl)butane, 2,3-dimethyl-2,3-di(4'-isopropylphenyl)butane, 3,4-di Methyl-3,4-diphenylhexane, 2,2,3,4,5,5-hexamethyl-3,4-diphenylhexane, 1,1,2,2-tetraphenyl Ethylene glycol, diisobutyl butyl 2,3-dicyano-2,3-diphenyl succinate or diethyl 2,3-dicyano-2,3-diphenyl succinate Any one or a mixture of at least two.
  • thermosetting resin composition further comprises a component (D) epoxy resin added in an amount of from 0 to 30 parts by mass and excluding 0, preferably from 2 to 27 parts by mass, further preferably from 5 to 25 parts by mass.
  • component (D) epoxy resin added in an amount of from 0 to 30 parts by mass and excluding 0, preferably from 2 to 27 parts by mass, further preferably from 5 to 25 parts by mass.
  • the amount of the epoxy resin added is, for example, 0.5 parts by mass, 1 part by mass, 3 parts by mass, 5 parts by mass, 7 parts by mass, 9 parts by mass, 11 parts by mass, 13 parts by mass, 15 parts by mass, 17 parts by mass, 19 parts by mass, 21 parts by mass, 23 parts by mass, 25 parts by mass, 27 parts by mass or 29 parts by mass.
  • the epoxy resin refers to an epoxy resin having two or more epoxy groups in one molecular resin, including a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a combination.
  • the mixture is, for example, a mixture of a bisphenol A type epoxy resin and a bisphenol F type epoxy resin, a mixture of a biphenyl type epoxy resin, a naphthalene type epoxy resin, and an alicyclic epoxy resin, and a resorcinol type.
  • thermosetting resin composition further comprises a component (E) curing agent added in an amount of from 0 to 10 parts by mass and not including 0, preferably from 0.5 to 9 parts by mass, further preferably from 1 to 8 parts by mass.
  • component (E) curing agent added in an amount of from 0 to 10 parts by mass and not including 0, preferably from 0.5 to 9 parts by mass, further preferably from 1 to 8 parts by mass.
  • the amount of the curing agent added is, for example, 0.5 parts by mass, 1 part by mass, 1.5 parts by mass, 2 parts by mass, 2.5 parts by mass, 3 parts by mass, 3.5 parts by mass, 4 parts by mass, 4.5 parts by mass, 5 parts by mass, 5.5. Parts by mass, 6 parts by mass, 6.5 parts by mass, 7 parts by mass, 7.5 parts by mass, 8 parts by mass, 8.5 parts by mass, 9 parts by mass Amount or 9.5 parts by mass.
  • thermosetting resin composition further comprises a component (F) curing accelerator added in an amount of 0 to 0.1 part by mass and not including 0, preferably 0.01 to 0.1 part by mass, further preferably 0.02 to 0.08 part by mass.
  • F component (F) curing accelerator added in an amount of 0 to 0.1 part by mass and not including 0, preferably 0.01 to 0.1 part by mass, further preferably 0.02 to 0.08 part by mass.
  • the amount of the curing accelerator added is, for example, 0.01 parts by mass, 0.015 parts by mass, 0.02 parts by mass, 0.025 parts by mass, 0.03 parts by mass, 0.035 parts by mass, 0.04 parts by mass, 0.045 parts by mass, 0.05 parts by mass, 0.055 parts by mass, 0.06 parts by mass, 0.065 parts by mass, 0.07 parts by mass, 0.075 parts by mass, 0.08 parts by mass, 0.085 parts by mass, 0.09 parts by mass or 0.095 parts by mass.
  • thermosetting resin composition further comprises a component (G) filler in an amount of 0 to 50 parts by mass and excluding 0, preferably 0.5 to 50 parts by mass, further preferably 3 to 47 parts by mass, further preferably 5 ⁇ 45 parts by mass.
  • a component (G) filler in an amount of 0 to 50 parts by mass and excluding 0, preferably 0.5 to 50 parts by mass, further preferably 3 to 47 parts by mass, further preferably 5 ⁇ 45 parts by mass.
  • the amount of the filler added is, for example, 0.1 parts by mass, 3 parts by mass, 5 parts by mass, 8 parts by mass, 11 parts by mass, 14 parts by mass, 17 parts by mass, 20 parts by mass, 23 parts by mass, 26 parts by mass, and 29 parts by mass. Parts, 32 parts by mass, 35 parts by mass, 38 parts by mass, 41 parts by mass, 44 parts by mass, 47 parts by mass or 49 parts by mass.
  • thermosetting resin composition further comprises a component (H) flame retardant, which may be a bromine- or phosphorus-containing organic compound in an amount such that the bromine content in the thermosetting resin composition is the total mass of the organic component. 5% to 15%, or the phosphorus content in the thermosetting resin composition is 0.6% to 2% of the total mass of the organic component.
  • H flame retardant
  • thermosetting resin composition means that it may include other components in addition to the components, and these other components impart different characteristics to the thermosetting resin composition.
  • the "include” of the present invention may also be replaced by a closed “for” or “consisting of”.
  • thermosetting 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, or a lubricant. Wait. These various additives may be used singly or in combination of two or more kinds.
  • Another object of the present invention is to provide a resin glue obtained by dissolving or dispersing the thermosetting resin composition as described above in a solvent.
  • the preparation method of the resin glue as described above is as follows:
  • component (A) and component (B) according to the formula amount, and raise the temperature to 125-160 ° C under stirring condition in the reaction flask. After the mixture becomes clear, the time reaction is 30-300 min, and 30 parts of DMF will be added.
  • the prepolymer is dissolved and allowed to cool to room temperature to give a clear modified double horse prepolymer which is then combined with component (C) with a free radical initiator and optionally an epoxy resin, optionally a curing agent, The curing accelerator, optionally the filler and optionally the flame retardant are optionally mixed uniformly to obtain a resin gum.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a thermosetting resin composition as described above adhered thereto by impregnation and drying.
  • the adhesive is impregnated with a reinforcing material such as E-glass cloth, and the impregnated reinforcing material is dried by heating in an oven at 155 ° C for 3 to 10 minutes to obtain a prepreg.
  • a reinforcing material such as E-glass cloth
  • a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fifth object of the present invention is to provide a printed wiring board comprising at least one prepreg as described above.
  • a sixth object of the present invention is to provide a metal foil-clad laminate comprising at least one prepreg as described above and a metal foil pressed on one or both sides of the laminated prepreg by heating Made by press forming.
  • An exemplary metal foil-clad laminate is prepared by laminating eight prepregs as described above, two-sided copper clad laminate, and laminating and curing at 218 ° C / 120 min in a hot press to obtain a metal foil-clad laminate.
  • the present invention has the following beneficial effects:
  • the present invention comprises a BMI modified with a diallyl bisphenol compound, an organic peroxide radical initiator having a one-hour half-life temperature of 110 to 150 ° C, a carbon-based radical initiator, optionally an epoxy resin, or A ground curing agent, optionally a curing accelerator, optionally a filler, and optionally a flame retardant are compounded to obtain a thermosetting resin resin composition.
  • the sheet obtained by using the thermosetting resin composition has excellent impact strength, bending strength, peel strength, and low Z-CTE.
  • DABPA Diallyl bisphenol A
  • BMI bismaleimide
  • Different modified bismaleimide prepolymers can be obtained by varying the ratio of diallyl bisphenol A to bismaleimide and the reaction time and reaction temperature.
  • the modified bismaleimide prepolymer and the complex free radical initiator and optionally an epoxy resin, optionally a curing agent, optionally a curing accelerator, optionally a filler, and optionally a flame retardant were uniformly mixed to obtain a resin glue.
  • the adhesive is impregnated with a reinforcing material such as E-glass cloth, and the impregnated reinforcing material is dried by heating in an oven at 155 ° C for 3 to 10 minutes to obtain a prepreg. Eight sheets of the prepreg as described above were laminated, and the copper foil was coated on both sides, and laminated and cured at 218 ° C / 120 min in a hot press to obtain a copper clad laminate.
  • Tables 1 to 5 below are the formulations and properties of the different examples and comparative examples.
  • TMA Thermomechanical Analysis

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Abstract

一种热固性树脂组合物及其用途。该热固性树脂组合物其按质量份数包括：（A）至少一种二烯丙基双酚类化合物，20质量份；（B）至少一种双马来酰亚胺化合物，24～80质量份；（C）复配自由基引发剂，0.5～5质量份；其中，所述复配自由基引发剂含有至少一种1小时半衰期的温度为110～150℃的有机过氧化物自由基引发剂以及至少一种碳系自由基引发剂。采用该热固性树脂组合物制得的板材具有优异的冲击强度、弯曲强度、剥离强度和低的Z-CTE。

Description

一种热固性树脂组合物及其用途 技术领域
本发明涉及一种热固性树脂组合物及其用途，具体涉及一种热固性树脂组合物、采用该树脂组合物的树脂胶液、预浸料、层压板以及印制线路板。
背景技术
BMI树脂通过DABPA改性后具有好的溶解性、韧性、工艺性等优点，但其在固化程中需要较高的温度和较长的时间以及较为苛刻的后处理条件才能满足其高性能要求。如下：
Figure PCTCN2015078591-appb-000001
由于BMI和DABPA中都含有碳-碳双键，可以通过自由基引发剂来加快双键的聚合，但是上图中的“ENE反应”和“D-A加成反应”的引发都需要与之温度相适应的自由基引发剂在相应的温度下引发聚合。
CN 01802158.1中用1小时半衰期温度为大于140℃有机过氧化物的引发剂引发双马来酰亚胺和聚烯烃的聚合，得到一种绝缘电力电缆。CN 03134502.6以1小时半衰期温度为80～140℃的有机过氧化物引发剂BPO或DCP为引发剂，引发双马来酰亚胺、DABPA、环氧树脂、环氧丙烯酸酯和活性稀释剂以制备耐高温复合材料。CN 101215358和CN 101215405中用反应温度为60～90℃的偶氮类引发剂或100～130℃的有机过氧化物引发剂或两者的复配来引 发MPGE和双马来酰亚胺的预聚。CN 101338047用1小时半衰期温度为130～140℃的有机过氧化物引发剂，引发丁腈橡胶和其助交联剂制备耐寒丁腈橡胶组合物。CN 101678643以1小时半衰期为100～150℃的有机过氧化物为引发剂，将氢化丁腈橡胶、双马来酰亚胺、多官能性不饱和化合物、抗老化剂等反应制得粘接剂。CN 101550248以有机过氧化物DCP为引发剂，将烯烃共聚物和硬脂酸锌、填料、炭黑和少量BMI混炼得到无卤阻燃聚烯烃弹性体。CN 102167825A以一小时半衰期为120～135℃的有机过氧化物TBPB/TAPB/DCP中的一种或几种做引发剂，于50～100℃下加入到DABPA/DDS/BMI的预聚体和相转移催化剂中，并与环氧混合制得树脂组合物用于制备碳纤维复合材料细杆。以上所有方案中都只用到了一种温度范围内的自由基引发剂，只能在较低温度范围内起到引发体系内的双键聚合。对高温下(大于200℃温度范围)的BMI的D-A加成反应无能为力，对提升固化体系的交联密度，从而改善体系的耐热性和热膨胀系数没有帮助。JP 2011225639A中以不同半衰期的有机过氧化物复配做引发剂，用在BMI改性PPO树脂体系中制得低CTE的层压板，此方案选择了几种1小时半衰期温度在180～200℃的有机过氧化氢作体系的复配引发剂中高温引发剂组分，但有机过氧化氢的引发温度相对BMI/DABPA树脂体系的D-A反应来说还是略低，其引发作用的时间较短；同时有机过氧化氢本身的沸点较低，在高温下容易挥发，特别是在CCL制作工艺过程中需要抽真空层压固化，使有机过氧化氢更容易从体系中逸出，从而达不到提升体系固化交联密度的作用从而无法对CCL的耐热性和热膨胀系数的改进有较大帮助。
发明内容
本发明的目的在于提供一种热固性树脂组合物，以及使用它的预浸料和印制电路用层压板。使用该树脂组合物制造的印制电路用层压板具有优异的冲击 强度、弯曲强度以及低的CTE。
为了达到上述目的，本发明采用了如下技术方案：
一种热固性树脂组合物，其按质量份数包括：
(A)至少一种二烯丙基双酚类化合物，20质量份；
(B)至少一种双马来酰亚胺化合物，24～80质量份；
(C)复配自由基引发剂，0.5～5质量份；
其中，所述复配自由基引发剂含有至少一种1小时半衰期的温度为110～150℃的有机过氧化物自由基引发剂以及至少一种碳系自由基引发剂；有机过氧化物自由基引发剂和碳系自由基发剂的质量比为1∶1～1∶9。
本发明通过自由基引发剂的复配，根据DABPA改性BMI(双马来酰亚胺)树脂聚合反应的原理，结合层压板的生产特点，即树脂组合物浸渍在玻纤布等增强材料上然后烘干，得到预浸料。在烘制过程中，温度为130～155℃，正是有机过氧化物自由基引发剂的起引发作用的温度范围。如上反应过程所示，在此温度下，有机过氧化物自由基引发剂(即低温引发剂)促进树脂体系中的双键发生初步的预聚(包括“ENE反应”和BMI中双键的自聚)，而碳系自由基引发剂(即高温引发剂)没有参加反应。同时在固化过程中，发生的D-A加成反应的温度为220℃左右。此温度远远超过了有机过氧化物的工作区间以及远远超过了有机过氧化物的沸点，在此温度区间内，有机过氧化物无法起到自由基引发剂的作用。同时，低温引发剂用量不能太大，以防止在此预聚反应时释放出大量气体，从而导致预浸料出现大量气孔的现象，以及避免预聚过度造成粘结片在压板固化时没有流动度，无法制成覆铜板。而碳系自由基引发剂的工作温度区域正在此区间内，能起到引发自由基聚合的作用，它能引发后续的D-A加成反应，以及低温烘片时多余的BMI中碳-碳双键的自聚。因为在低温 部分已经有部分发生反应，使碳-碳双键发生了初步预聚。并且，高温引发剂用量不大，且其固化是一个较长的过程，不会急剧产生气体导致覆铜板有大量气泡。本发明通过对两种上述两种引发剂的复配，能使最终的覆铜板的冲击强度和弯曲强度达到极大增强，并有效降低了板材Z-CTE。
所述组分(B)至少一种双马来酰亚胺化合物的含量为24～80质量份，例如为25质量份、27质量份、29质量份、31质量份、35质量份、37质量份、39质量份、41质量份、43质量份、45质量份、47质量份、49质量份、51质量份、53质量份、55质量份、57质量份、59质量份、61质量份、63质量份、65质量份、67质量份、69质量份、71质量份、73质量份、75质量份、77质量份或79质量份，优选28～76质量份，进一步优选32～72质量份。组分(B)双马来酰亚胺化合物的用量不同，可能得到不同的改性双马来酰亚胺预聚物，组分(B)双马来酰亚胺化合物的含量为24～80质量份时，通过复配的引发剂的使用都能够降低Z-CTE，提升冲击强度和弯曲强度。
优选地，所述二烯丙基双酚类化合物为二烯丙基二苯酚类化合物，选自二烯丙基双酚A、二烯丙基双酚F或二烯丙基双酚S中的任意一种或者至少两种的混合物。所述混合物例如二烯丙基双酚A和二烯丙基双酚F的混合物，二烯丙基双酚S和二烯丙基双酚A的混合物，二烯丙基双酚F和二烯丙基双酚S的混合物，二烯丙基双酚A、二烯丙基双酚F和二烯丙基双酚S的混合物。
优选地，所述双马来酰亚胺化合物为分子结构中含有两个马来酰亚胺基团的化合物，选自二苯甲烷双马来酰亚胺、二苯醚双马来酰亚胺或二苯砜双马来酰亚胺等中的任意一种或者至少两种的混合物。所述混合物例如二苯甲烷双马来酰亚胺和二苯醚双马来酰亚胺的混合物，二苯砜双马来酰亚胺和二苯甲烷双马来酰亚胺的混合物，二苯醚双马来酰亚胺和二苯砜双马来酰亚胺的混合物， 二苯甲烷双马来酰亚胺、二苯醚双马来酰亚胺和二苯砜双马来酰亚胺的混合物。
所述组分(C)复配自由基引发剂的含量为0.5～5质量份，例如为0.7质量份、0.9质量份、1.1质量份、1.3质量份、1.5质量份、1.7质量份、1.9质量份、2.1质量份、2.3质量份、2.5质量份、2.7质量份、2.9质量份、3.1质量份、3.3质量份、3.5质量份、3.7质量份、3.9质量份、4.1质量份、4.3质量份、4.5质量份、4.7质量份或4.9质量份，优选1.0～4.0质量份，进一步优选1.5～3.5质量份，更优选2.5～3.0质量份，最优选2.8～3.0质量份。在此引发剂用量范围内，即能使引发剂起到充分的引发作用，避免了过多的引发剂使自由基反应太快，导致在粘结片过程中树脂没有流动度，无法压制成合格的板材，同时还避免了过多引发剂反应后的小分子残留在体系中，使CCL的Td(5％loss)及耐热性下降。
为了避免有机过氧化物引发剂过多导致无法制成板材，以及碳系自由基引发剂过多导致耐热性下降，碳系自由基发剂和有机过氧化物自由基引发剂的质量比为1∶1～1∶9，例如1∶8.5、1∶8、1∶7.5、1∶7、1∶6.5∶、1∶6、1∶5.5、1∶5、1∶4.5、1∶4、1∶3.5、1∶3、1∶2.5、1∶2或1∶1.5，优选1∶2～1∶8，进一步优选1∶3～1∶7，更优选1∶4～1∶5，最优选1∶4.5～1∶5。
优选地，所述有机过氧化物自由基引发剂选自过氧化乙酸叔丁酯、过氧化马来酸叔丁酯、过氧化3，5，5-三甲基己酸叔丁酯、1，1-二(叔丁基过氧化)环己烷、2，2-二(叔丁基过氧化)丁烷、1，1-双(叔戊基过氧)环基烷、1，1-双(叔戊基过氧)-3，3，5-三甲基环已烷、过氧化2-乙基己基碳酸叔戊酯、过氧化醋酸叔戊酯、过氧化3，5，5三甲基己酸叔丁酯、过氧化二叔戊基、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基 过氧化)己烷、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔丁基过氧)丁酸乙酯、过氧化二异丙苯、双(叔丁基过氧化异丙基)苯、过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物。所述混合物例如过氧化乙酸叔丁酯和过氧化马来酸叔丁酯的混合物，过氧化3，5，5-三甲基己酸叔丁酯和1，1-二(叔丁基过氧化)环己烷的混合物，2，2-二(叔丁基过氧化)丁烷、1，1-双(叔戊基过氧)环基烷和1，1-双(叔戊基过氧)-3，3，5-三甲基环已烷的混合物，过氧化2-乙基己基碳酸叔戊酯、过氧化醋酸叔戊酯和过氧化3，5，5三甲基己酸叔丁酯的混合物，过氧化二叔戊基、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯和过氧化2-乙基己基碳酸叔丁酯的混合物，2，5-二甲基-2，5-双(叔丁基过氧化)己烷、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔丁基过氧)丁酸乙酯、过氧化二异丙苯和双(叔丁基过氧化异丙基)苯的混合物，过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷和过氧化叔丁基异丙苯的混合物。所述有机过氧化物自由基引发剂优选过氧化醋酸叔戊酯、过氧化3，5，5三甲基已酸叔丁酯、过氧化二叔戊基、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧化)己烷、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔丁基过氧)丁酸乙酯、过氧化二异丙苯、双(叔丁基过氧化异丙基)苯、过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物，进一步优选2，5-二甲基-2，5-双(叔丁基过氧化)己烷、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊 基过氧)丁酸乙酯、3，3-双(叔丁基过氧)丁酸乙酯、过氧化二异丙苯、双(叔丁基过氧化异丙基)苯、过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物，再优选过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物，最优选过氧化二叔丁基、过氧化二叔戊基或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物。
优选地，所述碳系自由基引发剂具有如下结构：
Figure PCTCN2015078591-appb-000002
其中，R1和R3相同，R1和R3同时选自苯基、取代或未取代的C1～C4的直链烷基或支链烷基或
Figure PCTCN2015078591-appb-000003
中的任意一种基团，其中R5为取代或未取代的C1～C4的直链烷基或支链烷基；
R2和R4相同，R2和R4同时选自-CN、-OH或取代或未取代的C1～C4的直链烷基或支链烷基中的任意一种基团；
X和Y独立地选自H、Br、Cl、苯基、取代或未取代的C1～C4的直链烷基或支链烷基、取代或未取代的C2～C4的直链烯基或支链烯基或——OR6中的任意一种基团，R6为取代或未取代的C1～C4的直链烷基或支链烷基或取代或未取代的C2～C4的直链烯基或支链烯基。
优选地，所述碳系自由基引发剂选自2，3-二甲基-2，3-二苯基丁烷、2，3-二甲 基-2，3-二(4`-甲基苯基)丁烷、2，3-二甲基-2，3-二(4`-异丙基苯基)丁烷、3，4-二甲基-3，4-二苯基己烷、2，2，3，4，5，5-六甲基-3，4-二苯基己烷、1，1，2，2-四苯基乙二醇、2，3-二氰基-2，3-二苯基丁二酸二异丁酯或2，3-二氰基-2，3-二苯基丁二酸二乙酯中的任意一种或者至少两种的混合物。
优选地，所述热固性树脂组合物还包括组分(D)环氧树脂，其添加量为0～30质量份且不包括0，优选2～27质量份，进一步优选5～25质量份。
所述环氧树脂的添加量例如为0.5质量份、1质量份、3质量份、5质量份、7质量份、9质量份、11质量份、13质量份、15质量份、17质量份、19质量份、21质量份、23质量份、25质量份、27质量份或29质量份。
优选地，所述环氧树脂是指在1个分子树脂中具有两个或两个以上环氧基团的环氧树脂，包括双酚A型环氧树脂、双酚F型环氧树脂、联苯型环氧树脂、萘类环氧树脂、脂环族类环氧树脂、间苯二酚型环氧树脂、聚乙二醇型环氧树脂、三官能团环氧树脂、溴化环氧树脂、四官能团环氧树脂或酚醛型环氧树脂中的任意一种或者至少两种的混合物。所述混合物例如双酚A型环氧树脂和双酚F型环氧树脂的混合物，联苯型环氧树脂、萘类环氧树脂和脂环族类环氧树脂的混合物，间苯二酚型环氧树脂、聚乙二醇型环氧树脂、三官能团环氧树脂和溴化环氧树脂的混合物，四官能团环氧树脂和酚醛型环氧树脂的混合物。
优选地，所述热固性树脂组合物还包括组分(E)固化剂，其添加量为0～10质量份且不包括0，优选0.5～9质量份，进一步优选1～8质量份。
所述固化剂的添加量例如为0.5质量份、1质量份、1.5质量份、2质量份、2.5质量份、3质量份、3.5质量份、4质量份、4.5质量份、5质量份、5.5质量份、6质量份、6.5质量份、7质量份、7.5质量份、8质量份、8.5质量份、9质 量份或9.5质量份。
优选地，所述热固性树脂组合物还包括组分(F)固化促进剂，其添加量为0～0.1质量份且不包括0，优选0.01～0.1质量份，进一步优选0.02～0.08质量份。
所述固化促进剂的添加量例如为0.01质量份、0.015质量份、0.02质量份、0.025质量份、0.03质量份、0.035质量份、0.04质量份、0.045质量份、0.05质量份、0.055质量份、0.06质量份、0.065质量份、0.07质量份、0.075质量份、0.08质量份、0.085质量份、0.09质量份或0.095质量份。
优选地，所述热固性树脂组合物还包括组分(G)填料，其添加量为0～50质量份且不包括0，优选0.5～50质量份，进一步优选3～47质量份，进一步优选5～45质量份。
所述填料的添加量例如为0.1质量份、3质量份、5质量份、8质量份、11质量份、14质量份、17质量份、20质量份、23质量份、26质量份、29质量份、32质量份、35质量份、38质量份、41质量份、44质量份、47质量份或49质量份。
优选地，所述热固性树脂组合物还包括组分(H)阻燃剂，其可以为含溴或含磷的有机化合物，添加量为使热固性树脂组合物中含溴量为有机组分总质量的5％～15％，或使热固性树脂组合物中含磷量为有机组分总质量的0.6％～2％。
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热固性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，所述热固性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。
本发明的目的之二在于提供一种树脂胶液，其是将如上所述的热固性树脂组合物溶解或分散在溶剂中得到。
如上所述的树脂胶液的制备方法为：
按配方量称取组分(A)和组分(B)，于反应瓶中，在搅拌条件下升温到125～160℃，待混合物变澄清后计时反应30～300min，加入30份的DMF将预聚物溶解，并降温到室温，得到透明的改性双马预聚物，然后将其与组分(C)复配自由基引发剂和任选地环氧树脂、任选地固化剂、任选地固化促进剂、任选地填料和任选地阻燃剂均匀混合，得到树脂胶液。
本发明的目的之三在于提供一种预浸料，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热固性树脂组合物。
使用该胶液含浸E-玻璃布等增强材料，将含浸好的增强材料在155℃的烘箱中加热干燥3～10分钟即可得到预浸料。
本发明的目的之四在于提供一种层压板，其包括至少一张如上所述的预浸料。
本发明的目的之五在于提供一种印制线路板，其包括至少一张如上所述的预浸料。
本发明的目的之六在于提供一种覆金属箔层压板，其包括至少一张如上所述的预浸料及压覆在叠合的预浸料一侧或两侧的金属箔，其通过加热加压成形而制得。
示例性的覆金属箔层压板的制备方法为：层叠8张如上所述的预浸料，两面覆铜箔，于热压机中按218℃/120min层压固化得到覆金属箔层压板。
与已有技术相比，本发明具有如下有益效果：
本发明通过将二烯丙基双酚类化合物改性的BMI、1小时半衰期温度为110～150℃有机过氧化物自由基引发剂、碳系自由基引发剂、任选地环氧树脂、任选地固化剂、任选地固化促进剂、任选地填料以及任选地阻燃剂复配，得到热固性树脂树脂组合物。采用该热固性树脂组合物制得的板材具有优异的冲击强度、弯曲强度、剥离强度和低的Z-CTE。
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。
按物质的量为1∶1.2称取二烯丙基双酚A(DABPA)和双马来酰亚胺(BMI)，将二烯丙基双酚A在搅拌条件下加热到100℃，然后将双马来酰亚胺加入其中，并搅拌，同时开始升温到预聚温度，当混合物变均一后继续反应相应的预聚时间，停止反应，并迅速倒出冷却，得到改性双马来酰亚胺预聚物。
改变二烯丙基双酚A和双马来酰亚胺的用量比以及反应时间和反应温度可以得到不同的改性双马来酰亚胺预聚物。
将改性双马来酰亚胺预聚物与复配自由基引发剂和任选地环氧树脂、任选地固化剂、任选地固化促进剂、任选地填料和任选地阻燃剂均匀混合，得到树脂胶液。使用该胶液含浸E-玻璃布等增强材料，将含浸好的增强材料在155℃的烘箱中加热干燥3～10分钟即可得到预浸料。层叠8张如上所述的预浸料，两面覆铜箔，于热压机中按218℃/120min层压固化得到覆铜板。
如下表1～5为不同实施例和对比例的配方以及性能。
表1
Figure PCTCN2015078591-appb-000004
Figure PCTCN2015078591-appb-000005
表2
Figure PCTCN2015078591-appb-000006
Figure PCTCN2015078591-appb-000007
表3
Figure PCTCN2015078591-appb-000008
Figure PCTCN2015078591-appb-000009
表4
Figure PCTCN2015078591-appb-000010
Figure PCTCN2015078591-appb-000011
表5
Figure PCTCN2015078591-appb-000012
Figure PCTCN2015078591-appb-000013
以上实施例和比较例皆参照IPC4101标准对覆铜板进行检测，检测方法如下：
CTE：热机械分析法(TMA)：IPC-TM-6502.4.24标准
弯曲强度：IPC-TM-6502.4.8标准
抗剥离强度：IPC-TM-6502.4.8标准
冲击强度：ISO-179-1-2010
玻璃化转变温度(Tg/DMA)：IPC-TM-6502.4.24.4标准
Td(5％loss)：IPC-TM-6502.4.24.6
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. 一种热固性树脂组合物，其特征在于，其按质量份数包括：
    (A)至少一种二烯丙基双酚类化合物，20质量份；
    (B)至少一种双马来酰亚胺化合物，24～80质量份；
    (C)复配自由基引发剂，0.5～5质量份；
    其中，所述复配自由基引发剂含有至少一种1小时半衰期的温度为110～150℃的有机过氧化物自由基引发剂以及至少一种碳系自由基引发剂；有机过氧化物自由基引发剂和碳系自由基发剂的质量比为1∶1～1∶9。
  2. 如权利要求1所述的热固性树脂组合物，其特征在于，所述组分(B)至少一种双马来酰亚胺化合物的含量为28～76质量份，优选32～72质量份；
    优选地，所述二烯丙基双酚类化合物为二烯丙基二苯酚类化合物，选自二烯丙基双酚A、二烯丙基双酚F或二烯丙基双酚S中的任意一种或者至少两种的混合物；
    优选地，所述双马来酰亚胺化合物选自二苯甲烷双马来酰亚胺、二苯醚双马来酰亚胺或二苯砜双马来酰亚胺中的任意一种或者至少两种的混合物。
  3. 如权利要求1或2所述的热固性树脂组合物，其特征在于，所述组分(C)复配自由基引发剂的含量为1.0～4.0质量份，优选1.5～3.5质量份，进一步优选2.5～3.0质量份，最优选2.8～3.0质量份；
    优选地，有机过氧化物自由基引发剂和碳系自由基发剂的质量比为1∶2～1∶8，优选1∶3～1∶7，更优选1∶4～1∶5，最优选1∶4.5～1∶5；
    优选地，所述有机过氧化物自由基引发剂选自过氧化乙酸叔丁酯、过氧化马来酸叔丁酯、过氧化3，5，5-三甲基己酸叔丁酯、1，1-二(叔丁基过氧化)环己烷、2，2-二(叔丁基过氧化)丁烷、1，1-双(叔戊基过氧)环基烷、1，1-双(叔戊基过氧)-3，3，5-三甲基环己烷、过氧化2-乙基己基碳酸叔戊酯、过氧化醋酸叔戊酯、 过氧化3，5，5三甲基己酸叔丁酯、过氧化二叔戊基、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧化)己烷、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔丁基过氧)丁酸乙酯、过氧化二异丙苯、双(叔丁基过氧化异丙基)苯、过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物，优选过氧化醋酸叔戊酯、过氧化3，5，5三甲基己酸叔丁酯、过氧化二叔戊基、过氧化苯甲酸叔丁酯、过氧化苯甲酸叔戊酯、过氧化2-乙基己基碳酸叔丁酯、2，5-二甲基-2，5-双(叔丁基过氧化)己烷、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔丁基过氧)丁酸乙酯、过氧化二异丙苯、双(叔丁基过氧化异丙基)苯、过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物，进一步优选2，5-二甲基-2，5-双(叔丁基过氧化)己烷、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔戊基过氧)丁酸乙酯、3，3-双(叔丁基过氧)丁酸乙酯、过氧化二异丙苯、双(叔丁基过氧化异丙基)苯、过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物，再优选过氧化二叔丁基、过氧化二叔戊基、2，5-二甲基-2，5-双(叔丁基过氧化)己炔-3、3，6，9-三乙基-3，6，9-三甲基-1，4，7-三过氧壬烷或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物，最优选过氧化二叔丁基、过氧化二叔戊基或过氧化叔丁基异丙苯中的任意一种或者至少两种的混合物；
    优选地，所述碳系自由基引发剂具有如下结构：
    Figure PCTCN2015078591-appb-100001
    其中，R1和R3同时选自苯基、取代或未取代的C1～C4的直链烷基或支链烷基或
    Figure PCTCN2015078591-appb-100002
    中的任意一种基团，其中R5为取代或未取代的C1～C4的直链烷基或支链烷基；
    R2和R4同时选自于-CN、-OH或取代或未取代的C1～C4的直链烷基或支链烷基中的任意一种基团；
    X和Y独立地选自H、Br、Cl、苯基、取代或未取代的C1～C4的直链烷基或支链烷基、取代或未取代的C2～C4的直链烯基或支链烯基或——OR6中的任意一种基团，R6为取代或未取代的C1～C4的直链烷基或支链烷基或取代或未取代的C2～C4的直链烯基或支链烯基；
    优选地，所述碳系自由基引发剂选自2，3-二甲基-2，3-二苯基丁烷、2，3-二甲基-2，3-二(4`-甲基苯基)丁烷、2，3-二甲基-2，3-二(4`-异丙基苯基)丁烷、3，4-二甲基-3，4-二苯基己烷、2，2，3，4，5，5-六甲基-3，4-二苯基己烷、1，1，2，2-四苯基乙二醇、2，3-二氰基-2，3-二苯基丁二酸二异丁酯或2，3-二氰基-2，3-二苯基丁二酸二乙酯中的任意一种或者至少两种的混合物。
  4. 如权利要求1-3之一所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括组分(D)环氧树脂，其添加量为0～30质量份且不包括0，优选2～27质量份，进一步优选5～25质量份；
    优选地，所述环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、联苯 型环氧树脂、萘类环氧树脂、脂环族类环氧树脂、间苯二酚型环氧树脂、聚乙二醇型环氧树脂、三官能团环氧树脂、溴化环氧树脂、四官能团环氧树脂或酚醛型环氧树脂中的任意一种或者至少两种的混合物。
  5. 如权利要求1-4之一所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括组分(E)固化剂，其添加量为0～10质量份且不包括0，优选0.5～9质量份，进一步优选1～8质量份；
    优选地，所述热固性树脂组合物还包括组分(F)固化促进剂，其添加量为0～0.1质量份且不包括0，优选0.01～0.1质量份，进一步优选0.02～0.08质量份。
  6. 如权利要求1-5之一所述的热固性树脂组合物，其特征在于，所述热固性树脂组合物还包括组分(G)填料，其添加量为0～50质量份且不包括0，优选0.5～50质量份，进一步优选3～47质量份，更优选5～45质量份；
    优选地，所述热固性树脂组合物还包括组分(H)阻燃剂；
    优选地，所述阻燃剂为含溴或含磷的有机化合物；
    优选地，所述阻燃剂的添加量为使热固性树脂组合物中含溴量为有机组分总质量的5％～15％，或使热固性树脂组合物中含磷量为有机组分总质量的0.6％～2％。
  7. 一种树脂胶液，其特征在于，其是将如权利要求1-6之一所述的热固性树脂组合物溶解或分散在溶剂中得到。
  8. 一种预浸料，其特征在于，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1-6之一所述的热固性树脂组合物。
  9. 一种层压板，其特征在于，其包括至少一张如权利要求8所述的预浸料。
  10. 一种印制线路板，其特征在于，其包括至少一张如权利要求8所述的 预浸料。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190369494A1 (en) * 2016-12-05 2019-12-05 Arkemea Inc. Initiator blends and photocurable compositions containing such initiator blends useful for 3d printing

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980706B (zh) * 2014-05-16 2017-01-11 广东生益科技股份有限公司 一种热固性树脂组合物及其用途
CN107672348A (zh) * 2017-09-27 2018-02-09 上海科灵文化用品有限公司 一种耐高温透明尺子
CN109734959B (zh) * 2018-12-17 2021-03-23 清远市普塞呋磷化学有限公司 一种耐温型自由基引发剂及其制备方法和应用
CN111040163B (zh) * 2019-11-29 2022-09-16 航天特种材料及工艺技术研究所 一种双马来酰亚胺树脂、热压罐成型用气囊及其制备方法
CN113461861B (zh) * 2021-07-20 2023-08-29 汕头市三马塑胶制品有限公司 一种新型环保功能化聚丙烯及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167825A (zh) * 2011-03-11 2011-08-31 南京航空航天大学 用于微径拉挤成型工艺的双马来酰亚胺树脂及其制备方法
CN103980706A (zh) * 2014-05-16 2014-08-13 广东生益科技股份有限公司 一种热固性树脂组合物及其用途

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61276808A (ja) * 1985-05-31 1986-12-06 Ube Ind Ltd マレイン酸変性ポリオレフィンの製造法
JPH09176246A (ja) * 1995-12-25 1997-07-08 Toyo Electric Mfg Co Ltd 一液性熱硬化性樹脂組成物
US8043534B2 (en) * 2005-10-21 2011-10-25 Designer Molecules, Inc. Maleimide compositions and methods for use thereof
CN101735456A (zh) * 2009-11-24 2010-06-16 广东生益科技股份有限公司 高耐热的热固性树脂组合物及采用其制作的半固化片及覆铜箔层压板
WO2013035205A1 (ja) * 2011-09-09 2013-03-14 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン アンダーフィル用組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102167825A (zh) * 2011-03-11 2011-08-31 南京航空航天大学 用于微径拉挤成型工艺的双马来酰亚胺树脂及其制备方法
CN103980706A (zh) * 2014-05-16 2014-08-13 广东生益科技股份有限公司 一种热固性树脂组合物及其用途

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, JIANXIN ET AL.: "The Properties and Applications of Carbon-Type Radical Activator", MODERN PLASTICS PROCESSING AND APPLICATIONS, vol. 14, no. 06, 30 May 2002 (2002-05-30), pages 4 - 42, XP055236265, ISSN: 1004-3055 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20190369494A1 (en) * 2016-12-05 2019-12-05 Arkemea Inc. Initiator blends and photocurable compositions containing such initiator blends useful for 3d printing

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