WO2018120472A1 - 一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板 - Google Patents

一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板 Download PDF

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Publication number
WO2018120472A1
WO2018120472A1 PCT/CN2017/078501 CN2017078501W WO2018120472A1 WO 2018120472 A1 WO2018120472 A1 WO 2018120472A1 CN 2017078501 W CN2017078501 W CN 2017078501W WO 2018120472 A1 WO2018120472 A1 WO 2018120472A1
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Prior art keywords
parts
weight
resin composition
halogen
free flame
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PCT/CN2017/078501
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English (en)
French (fr)
Inventor
奚龙
李江
许永静
Original Assignee
广东生益科技股份有限公司
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Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Priority to US15/736,998 priority Critical patent/US20180371232A1/en
Priority to KR1020177016428A priority patent/KR101980029B1/ko
Publication of WO2018120472A1 publication Critical patent/WO2018120472A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2425/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2435/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2479/00—Characterised by the use 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 C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C08K2201/00—Specific properties of additives
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • the present invention relates to the field of copper clad laminates, and more particularly to a halogen-free flame-retardant resin composition and a prepreg and copper-clad laminate thereof.
  • the industry usually uses phosphorus-containing resin or flame retardant, and combined with nitrogen-containing resin or flame retardant to achieve phosphorus-bromine synergistic and high-efficiency flame retardant.
  • the benzoxazine resin contains nitrogen and, when used in combination with phosphorus, achieves a V-0 rating of UL 94 with a lower phosphorus content.
  • the curing shrinkage rate is low, and the heat and humidity resistance is good, and it is widely used.
  • the ring-opening polymerization of benzoxazine requires higher temperature, which brings difficulties for industrial mass production and becomes a difficult point for its application.
  • US6509414A1 uses a brominated epoxy resin, tetrabromobisphenol A, and styrene-maleic anhydride to make a copper clad laminate. Since it contains a low C-Br bond energy, it is easy to cleave and release small molecules in an environment exceeding 200 ° C, resulting in a layered burst.
  • CN103421273A proposes to use benzoxazine resin, styrene-maleic anhydride, and biscyclopentadiene phenolic resin to cure epoxy resin to achieve low dielectric constant, low dielectric loss, high heat resistance and high flame resistance.
  • dicyclopentadiene phenolic resin there is no way The effect is to reduce the content of hydroxyl groups in the resin composition, and the dielectric constant dielectric loss of the composition is limited to a limited extent.
  • Both CN101684191B and C103131131A propose a co-curing epoxy of benzoxazine and styrene maleic anhydride, resulting in lower dielectric properties.
  • benzoxazine and styrene maleic anhydride are used as a composite curing agent for epoxy resins
  • the polymerization temperature of styrene maleic anhydride and epoxy is required to be lower, and benzoxazine and epoxy resin are required.
  • the temperature is higher.
  • the pressing temperature increases, the two main reactions of styrene maleic anhydride and epoxy, benzoxazine and epoxy will occur successively.
  • 2 to 3 clear will appear. Reaction exothermic peak.
  • benzoxazine is prone to self-polymerization at high temperatures, and this "complex" situation is likely to lead to reliability problems. Therefore, there has been a problem with the application of benzoxazine resins.
  • one of the objects of the present invention is to provide a halogen-free flame-retardant resin composition and a prepreg and copper-clad laminate thereof, which are greatly promoted by adding an acidic filler to the resin composition.
  • the polymerization of benzoxazine and epoxy resin reduces the curing temperature required for benzoxazine and epoxy polymerization; the better combination of alkylphenol epoxy resin and styrene maleic anhydride resin Electrical properties, and acidic fillers can make up for the defects of weak adhesion between layers, thus achieving synergy.
  • the inventors conducted intensive studies to achieve the above object, and found that a combination obtained by mixing an acidic filler with a benzoxazine resin, an alkylphenol epoxy resin, and styrene maleic anhydride, and optionally other substances.
  • the object can achieve the above purpose.
  • the present invention provides a halogen-free flame-retardant resin composition
  • a halogen-free flame-retardant resin composition comprising, by weight of the solid component, the following components:
  • (D) flame retardant 1 to 30 parts by weight
  • better dielectric properties can be achieved by the combination of an alkylphenol epoxy resin and a styrene maleic anhydride resin, and the addition of the acidic filler can compensate for the defects of weak interlayer adhesion, thereby achieving synergistic effect. It effectively improves the dielectric properties and peel strength stability of the resin composition, and provides excellent overall properties for prepregs and laminates for printed circuits.
  • the ring-opening polymerization reaction of the benzoxazine resin and the epoxy resin can be catalyzed, and the self-crosslinking polymerization of the benzoxazine can be promoted, thereby greatly reducing
  • the temperature required for the polymerization of benzoxazine and epoxy in addition, the melting point of the acidic filler can be as high as 1000 ° C or more, it will not be volatilized during the production of copper clad laminate, and will not decompose during PCB processing, and the organic acid is solved.
  • the acidic filler can also lower the CTE of the article in the resin composition, and its retention in the resin composition is beneficial to the reliability of the article.
  • the structure of the alkyl phenol epoxy resin is as follows:
  • R 1 and R 2 are independently a substituted or unsubstituted linear alkyl group or a branched alkyl group having 4 to 8 carbon atoms, such as n-butyl group, n-pentyl group, n-octyl group, isobutyl group, Isoamyl or the like, preferably n-butyl or n-octyl; n is an integer between 2 and 20, such as 2, 3, 4, 5, 6, 7, 8, 9, 12, 15, 18 or 20.
  • the content of the alkylphenol epoxy resin is 5 to 80 parts by weight, for example, 5 parts by weight, 10 parts by weight, 12 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, 40 parts by weight, 45 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight Part or 80 parts by weight, and the specific point values between the above values, are limited to the length and for the sake of brevity, the present invention is no longer exhaustive to enumerate the specific point values included in the range, preferably 10 to 35 parts by weight.
  • the benzoxazine resin or a compound having a dihydrobenzoxazine ring, is a benzo six-membered heterocyclic compound synthesized from phenol, primary amine and formaldehyde, and is subjected to ring opening.
  • the polymerization produces a nitrogen-containing and phenolic resin-like network.
  • the benzoxazine resin can improve the flame retardancy, moisture resistance, heat resistance and mechanical properties of the halogen-free flame-retardant resin composition, the prepreg obtained from the resin, the laminate, and the like. Higher glass transition temperature (Tg).
  • the benzoxazine resin is selected from the group consisting of bisphenol A type benzoxazine resin, dicyclopentadiene type benzoxazine resin, bisphenol F type benzoxazine resin, and phenolphthalein type benzoxazine.
  • any one or a mixture of at least two of a resin or MDA type benzoxazine resin wherein a typical but non-limiting mixture is: bisphenol A type benzoxazine resin and dicyclopentadiene type benzoxazine Resin, dicyclopentadiene type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol F type benzoxazine resin and phenolphthalein type benzoxazine resin.
  • R 3 is R 4 is -CH 2 - or Any one of them.
  • R 4 When R 4 is When the structural formula ( ⁇ ) is a bisphenol A type benzoxazine resin monomer; when R 4 is -CH 2 -, the structural formula ( ⁇ ) is a bisphenol F type benzoxazine resin monomer; when R 4 is When the structural formula ( ⁇ ) is a phenolphthalein type benzoxazine resin monomer.
  • the MDA type benzoxazine resin also known as a (4,4'-diaminodiphenylmethane) type benzoxazine resin, has a structure as shown by the formula ( ⁇ ):
  • the content of the benzoxazine resin in the halogen-free flame-retardant resin composition is 10 to 80 parts by weight, for example, 10 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, or 20 parts by weight. 22 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 32 parts by weight, 40 parts by weight, 45 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight or 80%
  • the parts by weight, and the specific point values between the above values, are limited in length and for the sake of brevity, the present invention is no longer exhaustive.
  • the specific point value included in the range is preferably 30 to 65 parts by weight.
  • the ratio of the styrene segment unit to the maleic anhydride segment unit in the styrene maleic anhydride resin is between 8:1 and 1:1.
  • 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1 or 1:1 the specific value between the above values, limited by space and for conciseness It is contemplated that the present invention is no longer exhaustive of the specific point values included in the scope.
  • the content of the styrene maleic anhydride resin in the halogen-free flame-retardant resin composition is 2 to 30 parts by weight, for example, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, or 12 parts by weight. Parts, 15 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 25 parts by weight, 28 parts by weight or 30 parts by weight, and specific points between the above values, limited to the length and for the sake of brevity, The invention is no longer exhaustive to enumerate the specific point values included in the ranges, and is preferably from 5 to 20 parts by weight.
  • the flame retardant is selected from the group consisting of resorcinol-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate), resorcinol-bis(2,6-dimethylphenyl) Any one or a mixture of at least two of a phosphate ester, a methyl dimethyl phosphate or a phosphazene compound, wherein a typical but non-limiting mixture is: resorcinol-bis(diphenyl phosphate) and double Phenol A-bis(diphenyl phosphate), bisphenol A-bis(diphenyl phosphate) and resorcinol-bis(2,6-dimethylphenyl phosphate), resorcinol-bis (2, 6-Dimethylphenyl phosphate) and dimethyl methyl phosphate, dimethyl methyl phosphate and phosphazene compounds.
  • the flame retardant is added in an amount of 1 to 30 parts by weight, for example, 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight.
  • Part, 28 parts by weight or 30 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 will not exhaustively enumerate the specific point values included in the range, preferably 3 to 20 weights. Share.
  • the acidic filler is selected from any one or a mixture of at least two of silicon micropowder, quartz powder, mica powder, clay, calcium oxalate or carbon black, wherein a typical but non-limiting mixture is silicon micropowder and Quartz powder, clay and calcium oxalate, carbon black and mica powder.
  • the acidic filler has a particle diameter of between 50 nm and 50 ⁇ m, such as 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 300 nm, 500 nm, 800 nm, 5 ⁇ m, 10 ⁇ m, 30 ⁇ m, 40 ⁇ m, 45 ⁇ m or 50 ⁇ m, 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 physical form of the acidic filler is not particularly limited, and may be, for example, a sheet, a rod, a sphere, a hollow sphere, a granule, a fiber or a plate; or a silane coupling agent may be optionally used for the acidic filler. Process it.
  • the acidic filler is added in an amount of 0.5 to 100 parts by weight, for example, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight.
  • Parts by weight, 40 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight or 100 parts by weight, and the specific values between the above values, are limited to the length and For the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the range, and is preferably from 5 to 60 parts by weight.
  • the present invention adopts an acidic filler in an amount of 5 to 60 as a preferred mode.
  • the filler is used in an amount exceeding 60 parts by weight, the resin composition is generally acidic, and the benzoxazine-epoxy system is used.
  • the ring-opening polymerization reaction is obviously accelerated, and the processing window of the resin composition is narrowed; if the amount of the acidic filler is less than 5 parts, the overall acidity of the resin composition is weak, and the catalysis of the benzoxazine-epoxy system is catalyzed. The effect is not obvious.
  • the pH of the acidic filler is between 2 and 6, for example 2, 2.5, 3, 3.5, 4, 5 or 6, and the specific values between the above values, limited by space and for simplicity It is contemplated that the present invention is no longer exhaustive of the specific point values included in the scope.
  • the acidic filler is characterized in that the filler and the deionized water are formulated into an aqueous solution at a mass ratio of 1:9, and the pH of the filler is obtained between 2 and 6.
  • the acidic filler of the present invention has a pH between 4 and 6.
  • the halogen-free flame-retardant resin composition may further contain a non-acidic filler.
  • the non-acidic filler is selected from any one or a mixture of at least two of calcium carbonate, calcium sulfate, aluminum oxide, barium sulfate, ceramic powder, talc or hydrotalcite, wherein a typical but non-limiting mixture For: calcium carbonate and calcium sulfate, alumina and barium sulfate, talc and ceramic powder.
  • the non-acid filler is added in an amount of 0 to 100 parts by weight, for example, 1 part by weight, 5 parts by weight, 15 parts by weight, 30 parts by weight, 45 parts by weight, 58 parts by weight, 62 parts by weight, 78 parts by weight.
  • 89 parts by weight or 100 parts by weight and the specific point values between the above values are limited, and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the ranges.
  • the halogen-free flame-retardant resin composition may further contain (F) a curing accelerator, which is 100 parts by weight of the organic solid matter in the halogen-free flame-retardant resin composition, and the curing accelerator
  • the amount added is 0.1 to 1 part by weight, for example, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight or 1 part by weight,
  • the specific point values between the above-mentioned values, and the present invention is not limited to the specific point values included in the scope.
  • the curing accelerator is selected from any one or a mixture of at least two of an imidazole accelerator and a derivative thereof, a pyridine accelerator or a Lewis acid accelerator, wherein a typical but non-limiting mixture It is an imidazole-promoting gold and pyridine accelerator, a pyridine accelerator, a Lewis acid accelerator, an imidazole accelerator, and a Lewis acid accelerator.
  • the imidazole promoter is selected from any one or at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole. mixture.
  • the curing accelerator is beneficial to the curing reaction of the epoxy resin and the benzoxazine resin and the curing agent to form a uniform three-dimensional network structure, to achieve better physical properties, and to promote hydroxyl (-OH) and epoxy groups.
  • a decrease in the concentration of the group which helps the resin composition achieve better dielectric properties, lower dielectric constant and Dielectric loss.
  • the halogen-free flame-retardant resin composition of the present invention comprises, by weight of the organic solids, the following components:
  • (D) flame retardant 3 to 20 parts by weight
  • (E) filler 5 to 60 parts by weight, the pH of which is between 2 and 6;
  • the preparation method of the halogen-free flame-retardant resin composition of the present invention can be selected by those skilled in the art with reference to the preparation method of the existing resin composition, and the actual situation is selected, and the present invention is not particularly limited.
  • the present invention also provides a method for preparing a halogen-free flame-retardant resin composition, which is:
  • the halogen-free flame-retardant resin composition contains an alkylphenol epoxy resin, a benzoxazine resin, and a styrene maleic anhydride resin.
  • the invention greatly promotes the polymerization reaction of benzoxazine and epoxy resin by adding an acidic filler to the halogen-free flame-retardant resin composition, and reduces the curing temperature required for benzoxazine and epoxy polymerization, so that The reaction of benzoxazine and epoxy is more complete; the laminate prepared by using the composition with added acidic filler has high peeling stability, high glass transition temperature, low water absorption, high heat resistance, and high Flexural strength and good processability, and can achieve a low coefficient of thermal expansion.
  • the present invention employs an alkylphenol epoxy resin which contributes to lowering the dielectric constant and dielectric loss factor of the system, and can increase the toughness of the composition and improve the quality of the drilled hole;
  • the combination of the resin and the styrene maleic anhydride resin can achieve better dielectric properties, and the addition of the acidic filler can make up for the defect that the interlayer bonding strength is weak, thereby achieving synergistic effect, which effectively enhances the resin composition. Dielectric properties and peel strength stability, and excellent composite properties for prepregs and laminates for printed circuits.
  • the halogen-free flame-retardant resin composition may optionally contain the present invention.
  • the component of the flame retardant, the non-acidic filler, and the curing accelerator according to the first aspect of the invention, and the respective components and contents contained in the halogen-free flame-retardant resin composition can be exemplarily referred to the present invention. The range described on the one hand.
  • the halogen-free flame-retardant 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. . These additives may be used singly or in combination of two or more.
  • halogen-free flame-retardant resin composition for the preparation steps of the halogen-free flame-retardant resin composition which is not further defined in the present invention, those skilled in the art can refer to the preparation method of the existing resin composition, and select it according to the actual situation, and the invention is not particularly limited.
  • the present invention also provides a prepreg comprising the halogen-free flame-retardant resin composition according to the first aspect, the halogen-free flame-retardant resin composition prepared according to the method of the second aspect, and a reinforcing material.
  • the reinforcing material to be used is not particularly limited and may be an organic fiber, an inorganic fiber woven cloth or a nonwoven fabric.
  • the organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth.
  • the thickness of the reinforcing material is not Particularly, in view of the good dimensional stability of the laminate, the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably is subjected to a fiber treatment and a surface treatment of a silane coupling agent, in order to provide good
  • the silane coupling agent is preferably any one or a mixture of at least two of an epoxy silane coupling agent, an aminosilane coupling agent or a vinyl silane coupling agent.
  • the prepreg is obtained by impregnating the above composite material by impregnation with the above composite material at 100 to 250 ° C for 1 to 15 minutes.
  • the copper-clad laminate for a printed circuit board of the present invention comprises a laminate obtained by bonding two or more prepregs together by heat and pressure, and bonded to one or both sides of the laminate.
  • the above copper foil; the copper-clad laminate lamination needs to meet the following requirements: 1.
  • the heating rate of the lamination is generally controlled at a temperature of 80-160 ° C at a temperature of 1.0 to 3.0 ° C / min; Pressure setting, the outer layer material temperature is applied at 80-100 ° C, the full pressure is about 300 psi; 3, when curing, the control material temperature is 185 ° C, and the temperature is kept for 90 min; the covered metal foil except copper foil
  • nickel foil, aluminum foil, SUS foil, etc. may be used, and the material is not limited.
  • the present invention has at least the following beneficial effects:
  • the present invention greatly promotes the polymerization of benzoxazine and an epoxy resin by adding an acidic filler to the halogen-free flame-retardant resin composition, and reduces the curing required for benzoxazine and epoxy polymerization.
  • the temperature makes the reaction of benzoxazine and epoxy more complete;
  • the laminate produced by using the halogen-free flame-retardant resin composition to which the acidic filler is added has high peeling stability, high glass transition temperature, low water absorption, high heat resistance, and high bending. Strength and good processability, and can achieve a low coefficient of thermal expansion;
  • the alkylphenol epoxy resin used in the present invention contains a large number of alkyl segments, which helps to lower the dielectric constant and dielectric loss factor of the system, and more alkyl segments will contribute to the increase.
  • the toughness of the composition improves the quality of the drill hole.
  • better dielectric properties can be achieved by using an alkylphenol epoxy resin together with styrene maleic anhydride, and the addition of an acidic filler can compensate for the interlayer adhesion. Weak defects, Thereby, the synergistic effect of the three is achieved, the dielectric properties and peel strength stability of the resin composition are effectively improved, and the laminate for prepreg and printed circuit board has excellent comprehensive performance.
  • the parts represent parts by weight, and the % represents "% by weight”.
  • A1 Alkylphenol epoxy resin, product of KES-7595 supplied by KOLON Korea
  • A2 DCPD epoxy, purchased from DIC model 7200H
  • F1 2-phenylimidazole purchased from the four countries of Japan.
  • laminates for printed circuit boards were prepared as follows, and the prepared laminates were subjected to performance tests.
  • the preparation method of the laminate for printed circuit board comprises:
  • step 2 8 pieces of prepreg and 2 pieces of one ounce (35 ⁇ m thick) metal foil are laminated together;
  • the operating conditions of the lamination are: when the temperature is 80-140 ° C, the controlled heating rate is 1.5-2.5 ° C / min; when the outer layer temperature is 80-100 ° C, the full pressure is applied, the full pressure is applied. It is about 350 psi; when curing, the temperature of the material is controlled at 195 ° C and kept for more than 60 minutes.
  • the measurement was carried out in accordance with the DSC method specified in 2.4.25 of IPC-TM-650.
  • Instrument manufacturer American TA. N2 environment, heating rate 10 ° C / min. The number of peaks between 100 ° C and 250 ° C on the DSC curve.
  • the measurement was carried out in accordance with the method specified in 2.4.24 of IPC-TM-650.
  • the dielectric constant and dielectric loss factor at 1 GHz were measured according to the method specified in 2.5.5.5 of IPC-TM-650 according to the resonance method using a strip line.
  • Example 3 Comparative Example 1, in which a styrene maleic anhydride tree was added After the fat, compared with the non-addition of styrene maleic anhydride in Comparative Example 1, the plate produced has a higher glass transition temperature, a lower dielectric loss factor, and better dielectric properties;
  • Example 3 and Comparative Example 2 For comparison, in Example 3, an alkylphenol epoxy resin was added, and when the epoxy resin was not added in Comparative Example 2 and replaced with another epoxy resin, the dielectric loss factor of the sheet produced was lower. The electrical properties were better;
  • Example 3 was compared with Comparative Example 3, by adding an acidic filler having a pH between 2 and 6 in comparison with the DSC peak of Comparative Example 3 when no filler was added. The number is small, and the plate made thereof has a higher glass transition temperature, a lower water absorption rate, a higher peel strength, and a lower dielectric loss factor.
  • Example 3 Comparative Example 3 by adding an acidic filler having a pH between 2 and 6, an acidity having a pH greater than 6 was added in Comparative Example 4-5.
  • an acidic filler having a pH between 2 and 6 an acidity having a pH greater than 6 was added in Comparative Example 4-5.
  • the filler is used, the number of DSC peaks is small, and the plate produced thereof has a higher peeling strength; when the alkaline filler is added in Comparative Example 6, the number of DSC peaks is small, and the plate made thereof has more High glass transition temperature and high peel strength.
  • Example 3 and Comparative Examples 4-6 in the present invention, by using an acidic filler having a pH between 2 and 6, it greatly promotes the polymerization of benzoxazine and epoxy resin, and reduces The curing temperature required for benzoxazine and epoxy polymerization makes the reaction of benzoxazine and epoxy more complete, and the laminate has high anti-peeling stability, high glass transition temperature and low water absorption. Rate, high heat resistance, high bending strength and good processability, and can achieve a low coefficient of thermal expansion.
  • Example 5-6 Comparing Examples 5-6 with Examples 7-8, the amount of the acidic filler added in Example 5-6 by controlling the addition amount of the acidic filler to 5 to 60 parts by weight as compared with Example 7.
  • the amount is less than 5 parts by weight, the number of DSC peaks is small, the catalyst has more excellent catalysis, the glass transition temperature is higher, and the V-0 grade flame retardant is achieved, the water absorption rate is low, the peel strength is higher, and the heat expansion is low.
  • Coefficient when the amount of the acidic filler added is more than 60 parts by weight compared to Example 8, it has higher peel strength and good workability.
  • the halogen-free flame-retardant resin composition provided by the present invention can effectively improve the dielectric properties and peel strength of the resin composition while ensuring a high glass transition temperature and excellent heat and humidity resistance. Properties; and provide excellent overall performance for prepreg and copper clad laminates.

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Abstract

本发明涉及一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板，以固体组分重量份计，包括如下组分：(A)烷基苯酚环氧树脂：5～80重量份；(B)苯并噁嗪树脂：10～80重量份；(C)苯乙烯马来酸酐树脂：2～30重量份；(D)阻燃剂：1～30重量份；(E)酸性填料：0.5～100重量份，其pH在2～6之间。本发明还提供了用所述无卤阻燃型树脂组合物制备的预浸料和覆铜箔层压板。本发明提供的无卤阻燃型树脂组合物在保证具有较高玻璃化转变温度，优良耐湿热性的同时，有效提升了树脂组合物的介电性能和剥离强度稳定性；并使预浸料和覆铜箔层压板具有优异的综合性能。

Description

一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板 技术领域
本发明涉及覆铜板技术领域，尤其涉及一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板。
背景技术
为实现无溴阻燃，业内通常采用含磷的树脂或阻燃剂，配合含氮的树脂或阻燃剂实现磷-溴协同高效阻燃。苯并噁嗪树脂中含有氮元素，与磷元素复配使用时，可以较低的磷含量实现UL 94的V-0等级。加之固化收缩率低，耐湿热性能佳，得到了广泛使用。然而，由于苯并噁嗪树脂结构特点，苯并噁嗪的开环聚合需要较高的温度，为工业化批量生产带来了困难，成为了其应用的难点。
随着通讯技术的发展，对印制线路基板(CCL)介电常数(Dk)和介电损耗的要求越来越高。众所周知，Dk越低，Df越小，信号在基板上传输的速度越快，信号在传输过程中损失功率保持一致时，容许传输的频率就越高。此外，以手机，笔记本电脑，平板电脑为代表的消费电子领域，轻薄短小这一趋势将会进一步发展。为实现更薄的设计且不降低运算速度，必须开发具有较低介电常数/介电损耗的基板。近年来，越来越多的业内研究均关注如何降低基板材料的介电常数/介电损耗。
US6509414A1使用溴化环氧树脂，四溴双酚A，以及苯乙烯-马来酸酐制作覆铜板。由于其含有的C-Br键键能较低，容易在超过200℃的环境中断裂释放出小分子，导致分层爆板。CN103421273A提出了采用苯并噁嗪树脂，苯乙烯-马来酸酐，以及双环戊二烯酚醛树脂固化环氧树脂，达到低介电常数，低介电损耗，高耐热，高耐燃的性能。然而由于双环戊二烯酚醛树脂的使用，无法有 效降低树脂组合物中羟基的含量，组合物的介电常数介电损耗降低的幅度有限。
CN101684191B和C103131131A均提出了苯并噁嗪和苯乙烯马来酸酐共同固化环氧，得到了较低的介电性能。然而苯并噁嗪和苯乙烯马来酸酐作为环氧树脂的复合固化剂时，苯乙烯马来酸酐和环氧的聚合反应所需温度较低，而苯并噁嗪和环氧树脂所需的温度较高。随着压合温度升高，苯乙烯马来酸酐和环氧，苯并噁嗪和环氧这两个主要反应将会先后发生，在差热扫描分析图上，将出现2～3个清晰的反应放热峰。而且，苯并噁嗪在高温时容易发生自聚反应，这一“复杂”局面容易带来可靠性方面的隐患。因此，对于苯并噁嗪树脂的应用，一直存在难题。
发明内容
基于此，本发明的目的之一在于提供一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板，通过在树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度；通过烷基苯酚环氧树脂和苯乙烯马来酸酐树脂的配合能实现更好的介电性能，并且酸性填料可弥补其层间结合力弱的缺陷，从而实现协同增效。
发明人为实现上述目的，进行了反复深入的研究，结果发现：通过将酸性填料与苯并噁嗪树脂、烷基苯酚环氧树脂和苯乙烯马来酸酐以及可选的其他物质进行混合得到的组合物，可达到上述目的。
为了实现上述目的，本发明采用了如下技术方案：
第一方面，本发明提供了一种无卤阻燃型树脂组合物，以固体组分重量份计，包括如下组分：
(A)烷基苯酚环氧树脂：5～80重量份；
(B)苯并噁嗪树脂：10～80重量份；
(C)苯乙烯马来酸酐树脂：2～30重量份；
(D)阻燃剂：1～30重量份；
(E)酸性填料：0.5～100重量份，其pH值在2～6之间。
本发明中通过烷基苯酚环氧树脂和苯乙烯马来酸酐树脂的配合能实现更好的介电性能，并且酸性填料的添加可弥补其层间结合力弱的缺陷，从而实现协同增效作用，其有效提升了树脂组合物的介电性能和剥离强度稳定性，并使预浸料、印制电路用层压板具有优异的综合性能。
本发明中通过在无卤阻燃型树脂组合物中添加酸性填料，可以催化苯并噁嗪树脂和环氧树脂的开环聚合反应，又能促进苯并噁嗪自身交联聚合，极大地降低了苯并噁嗪和环氧聚合所需的温度；另外，酸性填料的熔点可高达1000℃以上，在覆铜板生产过程中受热不会挥发，在PCB加工中也不会分解，解决了有机酸和普通无机酸在树脂中的弱点；再有，酸性填料在树脂组合物中还能降低制品的CTE，其在树脂组合物中保留下来对制品的可靠性有益。
根据本发明，所述烷基苯酚环氧树脂的结构如下所示：
Figure PCTCN2017078501-appb-000001
其中，R1，R2独立地为取代或未取代的碳原子数为4～8的直链烷基或支链烷基，例如正丁基、正戊基、正辛基、异丁基、异戊基等，优选正丁基或正辛基；n为2～20之间的整数，例如2、3、4、5、6、7、8、9、12、15、18或20。
本发明所述无卤阻燃型树脂组合物中，烷基苯酚环氧树脂的含量为5～80重量份，例如5重量份、10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、40重量份、45重量份、55重量份、60重量份、65重量份、70重量份、75重量份或80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10～35重量份。
根据本发明，所述苯并噁嗪树脂，或称具有二氢苯并噁嗪环的化合物，是由酚、伯胺和甲醛为原料合成的一种苯并六元杂环化合物，经开环聚合可生成含氮且类似酚醛树脂的网状结构。本发明中，苯并噁嗪树脂能够提高无卤阻燃型树脂组合物及由所述树脂得到的预浸料、层压板等所需的阻燃性能、耐湿性、耐热性、力学性能及较高的玻璃转变温度(Tg)。
本发明中，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA型苯并噁嗪树脂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：双酚A型苯并噁嗪树脂和双环戊二烯型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂和双酚F型苯并噁嗪树脂、双酚F型苯并噁嗪树脂和酚酞型苯并噁嗪树脂。
所述双酚A型苯并噁嗪树脂单体和双酚F型苯并噁嗪树脂单体、酚酞型苯并噁嗪树脂单体的结构如式(α)所示：
Figure PCTCN2017078501-appb-000002
其中，R3为
Figure PCTCN2017078501-appb-000003
R4为
Figure PCTCN2017078501-appb-000004
-CH2-或
Figure PCTCN2017078501-appb-000005
中的任意1种。
当R4为
Figure PCTCN2017078501-appb-000006
时，结构式(α)为双酚A型苯并噁嗪树脂单体；当R4为-CH2-时，结构式(α)为双酚F型苯并噁嗪树脂单体；当R4为
Figure PCTCN2017078501-appb-000007
时，结构式(α)为酚酞型苯并噁嗪树脂单体。
所述MDA型苯并噁嗪树脂，又称(4，4’-二胺基二苯甲烷)型苯并噁嗪树脂，其结构如式(β)所示：
Figure PCTCN2017078501-appb-000008
所述双环戊二烯苯并噁嗪树脂单体的结构式如(γ)所示：
Figure PCTCN2017078501-appb-000009
根据本发明，所述无卤阻燃型树脂组合物中，苯并噁嗪树脂的含量为10～80重量份，例如10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、40重量份、45重量份、55重量份、60重量份、65重量份、70重量份、75重量份或80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30～65重量份。
在本发明所述无卤阻燃型树脂组合物中，所述苯乙烯马来酸酐树脂中苯乙烯链段单元和马来酸酐链段单元的比例介于8∶1～1∶1之间，例如8∶1、7∶1、6∶1、5∶1、4∶1、3∶1、2∶1或1∶1，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。
根据本发明，所述无卤阻燃型树脂组合物中，苯乙烯马来酸酐树脂的含量为2～30重量份，例如2重量份、5重量份、8重量份、10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重量份或30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5～20重量份。
本发明中，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2，6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：间苯二酚-双(磷酸二苯酯)和双酚A-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)和间苯二酚-双(2，6-二甲苯基磷酸酯)、间苯二酚-双(2，6-二甲苯基磷酸酯)和甲基磷酸二甲酯、甲基磷酸二甲酯和磷腈化合物。
根据本发明，所述阻燃剂的添加量为1～30重量份，例如1重量份、2重量份、5重量份、8重量份、10重量份、15重量份、20重量份、25重量份、28重量份或30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3～20重量份。
本发明中，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为硅微粉和石英粉、黏土和草酸钙、炭黑和云母粉。
本发明中，所述酸性填料的粒径在50nm～50μm之间，例如50nm、60nm、70nm、80nm、90nm、100nm、300nm、500nm、800nm、5μm、10μm、30μm、40μm、45μm或50μm，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。
对于所述酸性填料的物理形态，本发明不做特殊限定，例如可以是片材、棒状、球形、空心球形、粒状、纤维状或板状等；也可以选择性以硅烷偶联剂对酸性填料进行处理。
根据本发明，所述无卤阻燃型树脂组合物中，酸性填料的添加量为0.5～100重量份，例如0.5重量份、0.8重量份、1重量份、10重量份、20重量份、30重量份、40重量份、55重量份、60重量份、65重量份、70重量份、80重量份、90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5～60重量份。
本发明采用酸性填料的添加量为5～60作为优选方式，经发明人研究发现，若所述填料使用量超过60重量份，树脂组合物整体酸性较强，苯并噁嗪-环氧体系的开环聚合反应明显加快，会使得树脂组合物的加工工艺窗口变窄；若所述酸性填料使用量低于5份，树脂组合物整体酸性较弱，对苯并噁嗪-环氧体系的催化作用不明显。
根据本发明，所述酸性填料的pH值在2～6之间，例如2、2.5、3、3.5、4、5或6，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，所述酸性填料的特征是：将该填料与去离子水按1∶9的质量比配制成水溶液，对其进行测定从而得到该填料的pH值在2～6之间。
优选地，本发明所述酸性填料的pH值在4～6之间。
根据本发明，所述无卤阻燃型树脂组合物中还可以含有非酸性填料。
优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为：碳酸钙和硫酸钙、氧化铝和硫酸钡、滑石粉和陶瓷粉。
优选地，所述非酸性填料的添加量为0～100重量份，例如1重量份、5重量份、15重量份、30重量份、45重量份、58重量份、62重量份、78重量份、89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。
根据本发明，所述无卤阻燃型树脂组合物中还可以含有(F)固化促进剂，以无卤阻燃型树脂组合物中有机固形物为100重量份计，所述固化促进剂的添加量为0.1～1重量份，例如0.1重量份、0.2重量份、0.3重量份、0.4重量份、0.5重量份、0.6重量份、0.7重量份、0.8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。
本发明中，所述固化促进剂选自咪唑类促进剂及其衍生物、吡啶类促进剂或路易斯酸类促进剂中的任意一种或至少两种的混合物，其中典型但非限制性的混合物为咪唑类促进金和吡啶类促进剂、吡啶类促进剂和路易斯酸类促进剂、咪唑类促进剂和路易斯酸类促进剂。
优选地，所述咪唑类促进剂选自2-甲基咪唑、2-乙基_4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的任意一种或至少两种的混合物。
所述固化促进剂有益于环氧树脂和苯并噁嗪树脂以及固化剂进行固化反应，形成均匀的三维网状分子结构，达到较佳的物性，并能促进羟基(-OH)和环氧基等基团浓度的下降，帮助树脂组合物实现较佳的介电性能，降低介电常数和 介电损耗。
作为优选技术方案，本发明所述无卤阻燃型树脂组合物，以有机固形物重量份计，包括如下组分：
(A)环氧树脂：10～35重量份；
(B)苯并噁嗪树脂：30～60重量份；
(C)苯乙烯马来酸酐树脂：5～20重量份；
(D)阻燃剂：3～20重量份；
(E)填料：5～60重量份，其pH值在2～6之间；
(F)固化促进剂：0.1～1重量份。
本发明所述无卤阻燃型树脂组合物的制备方法，本领域技术人员可以参考现有的树脂组合物的制备方法，结合实际情况进行选择，本发明不做特殊限定。
第二方面，本发明还提供了一种无卤阻燃型树脂组合物的制备方法，所述方法为：
向所述无卤阻燃型树脂组合物中添加pH值介于2～6的酸性填料；
所述无卤阻燃型树脂组合物中含有烷基苯酚环氧树脂、苯并噁嗪树脂和苯乙烯马来酸酐树脂。
本发明通过在无卤阻燃型树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使苯并噁嗪和环氧的反应更完全；通过使用该添加有酸性填料的组合物制作的层压板具有高的抗剥稳定性，高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。
本发明通过采用烷基苯酚环氧树脂，其有助于降低体系的介电常数和介电损耗因子，并可增加组合物的韧性，改善钻孔质量；同时，通过烷基苯酚环氧 树脂和苯乙烯马来酸酐树脂的配合能实现更好的介电性能，并且酸性填料的添加可弥补其层间结合力弱的缺陷，从而实现协同增效作用，其有效提升了树脂组合物的介电性能和剥离强度稳定性，并使预浸料、印制电路用层压板具有优异的综合性能。
本领域技术人员可以明了，所述无卤阻燃型树脂组合物的制备方法中除了烷基苯酚环氧树脂、苯并噁嗪树脂和苯乙烯马来酸酐树脂外，还可以任选地含有本发明第一方面所述的阻燃剂、非酸性填料以及固化促进剂等组分，且所述无卤阻燃型树脂组合物中含有的各个组分和含量均可示例性地参考本发明第一方面所述的范围。
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，所述无卤阻燃型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。这些添加剂可以单独使用，也可以两种或者两种以上混合使用。
对于本发明中未进一步限定的无卤阻燃型树脂组合物的制备步骤，本领域技术人员可以参考现有的树脂组合物的制备方法，结合实际情况进行选择，本发明不做特殊限定。
本发明还提供了一种预浸料，其含有第一方面所述的无卤阻燃型树脂组合物根据第二方面所述的方法制备得到的无卤阻燃型树脂组合物，以及增强材料；所使用的增强材料无特别的限定，可以为有机纤维、无机纤维编织布或无纺布。所述的有机纤维可以选择芳纶无纺布，所述的无机纤维编织布可以为E-玻纤布、D-玻纤布、S-玻纤布、T玻纤布、NE-玻纤布或石英布。所述增强材料的厚度无 特别限定，处于层压板有良好的尺寸稳定性的考虑，所述编织布及无纺布厚度优选0.01～0.2mm，且最好是经过开纤处理及硅烷偶联剂表面处理的，为了提供良好的耐水性和耐热性，所述硅烷偶联剂优选为环氧硅烷偶联剂、氨基硅烷偶联剂或乙烯基硅烷偶联剂中的任意一种或至少两种的混合物。将增强材料通过含浸上述的复合材料，在100～250℃条件下，烘烤1～15分钟得到所述预浸料。
本发明的印刷电路板用覆铜箔层压板包括通过加热和加压，使两片或两片以上的预浸料粘合在一起而制成的层压板、粘合在层压板的一面或两面以上的铜箔；所述的覆铜箔层压需满足以下要求：1、层压的升温速率通常在料温80～160℃时的升温速度应控制在1.0～3.0℃/min；2、层压的压力设置，外层料温在80～100℃时施加满压，满压压力为300psi左右；3、固化时，控制料温在185℃，并保温90min；所覆盖的金属箔除铜箔外，还可以是镍箔、铝箔及SUS箔等，其材质不限。
与现有技术相比，本发明至少具有以下有益效果：
(1)本发明通过在无卤阻燃型树脂组合物中添加酸性填料，极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使苯并噁嗪和环氧的反应更完全；
(2)本发明通过使用该添加有酸性填料的无卤阻燃型树脂组合物制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数；
(3)本发明采用的烷基苯酚环氧树脂含有较多的烷基链段，有助于降低体系的介电常数和介电损耗因子，同时较多的烷基链段将有助于增加组合物韧性，改善钻孔质量，另外，通过将烷基苯酚环氧树脂与苯乙烯马来酸酐二者配合使用能实现更好的介电性能，并且酸性填料的添加可弥补其层间结合力弱的缺陷， 从而实现三者的协同增效作用，有效提升了树脂组合物的介电性能和剥离强度稳定性，并使预浸料、印制电路用层压板具有优异的综合性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
以下所述是本发明实施例的具体实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明实施例原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明实施例的保护范围。
下面分多个实施例对本发明实施例进行进一步的说明。本发明实施例不限定于以下的具体实施例。在不改变权利要求的范围内，可以适当的进行变更实施。
下文中如无特别说明，其份代表重量份，其％代表“重量％”。
实施例和对比例涉及的材料及牌号信息如下：
(A)环氧树脂：
A1：烷基苯酚环氧树脂，韩国KOLON提供的商品型号为KES-7595的产品
A2：DCPD环氧，购于DIC的型号为7200H的产品
(B)苯并噁嗪树脂：
B1：购于亨斯迈的型号为LZ8290H62的产品
B2：购于东材科技的型号为D125的产品
(C)苯乙烯马来酸酐树脂：
C1：购于沙多玛的型号为EF40的产品
C2：购于沙多玛的型号为EF60的产品
(D)阻燃剂
D1：购于日本大八化学的型号为PX-200的产品
D2：购于日本大塚化学株式会社的型号为SPB-100的产品
(E)填料
E1：购于江苏联瑞的二氧化硅DQ-1030，pH＝4.0
E2：购于安徽格锐云母粉GD-2，pH＝5.0
E3：购于天津星龙泰化工产品科技有限公司的炭黑，pH＝3.0
E4：购于蚌埠鑫源的勃姆石BG-615，pH＝6.8
E5：购于矽比科的二氧化硅MEGASIL525，pH＝6.5
E6：购于日本admatechs球形硅微粉SC2500-SEJ，pH＝8.0
(F)固化促进剂
F1：购于日本四国化成的2-苯基咪唑。
将实施例和对比例提供的树脂组合物，按照如下方法制备印制电路用层压板，并对制备得到的层压板进行性能测试。
所述印制电路用层压板的制备方法包括：
①通过加热和加压作用使一张或一张以上的预浸料粘合在一起，制成的层压板；
②在步骤①制得的层压板的一面或两面上粘合金属箔；
③在层压机中进行层压；
在步骤②的过程中，使用8片预浸料和2片一盎司(35μm厚)的金属箔叠合在一起；
在步骤③的过程中，层压的操作条件为：料温80～140℃时，控制升温速率为1.5～2.5℃/min；外层料温80-100℃时，施加满压，满压压力为350psi左右；固化时，控制料温在195℃，并保温60min以上。
实施例和对比例提供的树脂组合物的配方及性能测试结果见表1～3。
表1
Figure PCTCN2017078501-appb-000010
表2
Figure PCTCN2017078501-appb-000011
Figure PCTCN2017078501-appb-000012
表3
Figure PCTCN2017078501-appb-000013
Figure PCTCN2017078501-appb-000014
性能测试的项目及具体方法为：
(a)玻璃化转变温度：
根据差示扫描量热法，按照IPC-TM-650中2.4.25所规定的DSC方法进行测定。
(b)耐燃烧性：
依据UL94法测定。
(c)吸水性：
按照IPC-TM-650中的2.6.2.1所规定的方法进行测定。
(d)DSC峰个数：
仪器商：美国TA。N2环境，升温速率10℃/min。DSC曲线上，100℃～250℃之间的峰的个数。
(e)剥离强度：
按照IPC-TM-650中的2.4.8所规定的方法进行测定。
(f)热膨胀系数：
按照IPC-TM-650中的2.4.24所规定的方法进行测定。
(g)介电常数和介电损耗因素
根据使用条状线的共振法，按照IPC-TM-650中的2.5.5.5所规定的方法测定1GHz下的介电常数和介电损耗因素。
物性分析：
(1)将实施例3与对比例1进行比较，实施例3中添加苯乙烯马来酸酐树 脂后，相比对比例1中未添加苯乙烯马来酸酐时，其制成的板材玻璃化转变温度较高，介电损耗因子较低，介电性能更好；将实施例3与对比例2进行比较，实施例3中添加烷基苯酚环氧树脂，相比对比例2中未添加该环氧树脂而替换为其他环氧树脂时，其制成的板材介电损耗因子较低，介电性能更好；将实施例3与对比例3进行比较，实施例3中通过添加pH值介于2-6之间的酸性填料，相比对比例3中未添加填料时，其DSC峰个数少，并且其制成的板材具有更高的玻璃化转变温度，吸水率低，具有更高的剥离强度，介电损耗因子较低。
由上述实施例和对比例可以看出，本发明中通过将烷基苯酚环氧树脂与苯乙烯马来酸酐二者配合使用能实现更好的介电性能，并且酸性填料的添加可弥补其层间结合力弱的缺陷，从而实现三者的协同增效作用，有效提升了树脂组合物的介电性能和剥离强度稳定性，并使预浸料、印制电路用层压板具有优异的综合性能。
(2)将实施例3与对比例4-6进行比较，实施例3中通过添加pH值介于2-6之间的酸性填料，相比对比例4-5中添加pH值大于6的酸性填料时，其DSC峰个数少，并且其制成的板材具有更高的剥离强度；相比对比例6中添加碱性填料时，其DSC峰个数少，并且其制成的板材具有更高的玻璃化转变温度和高剥离强度。
通过实施例3与对比例4-6可以看出，本发明中通过采用pH值介于2-6之间的酸性填料，其极大地促进了苯并噁嗪和环氧树脂的聚合反应，降低了苯并噁嗪和环氧聚合所需的固化温度，使苯并噁嗪和环氧的反应更完全，同时使制作的层压板具有高的抗剥稳定性、高玻璃化转变温度、低吸水率、高耐热性、高弯曲强度和良好的工艺加工性，并能实现低热膨胀系数。
(3)将实施例9与对比例7进行比较，实施例9中采用将烷基苯酚环氧树 脂控制在较低含量时，其能使板材具有高玻璃化转变温度，可达到V-0级阻燃，吸水率低，具有更高的剥离强度、低热膨胀系数以及更低的介电损耗因子。
(4)将实施例5-6和实施例7-8进行比较，实施例5-6通过将酸性填料的添加量控制在5-60重量份时，相比实施例7将酸性填料的添加量低于5重量份时，其DSC峰个数少，具有更优异的催化作用，玻璃化转变温度更高，并能达到V-0级阻燃，吸水率低、剥离强度更高，具有低热膨胀系数；相比实施例8将酸性填料的添加量高于60重量份时，其具有更高的剥离强度，加工性能好。
综合上述结果可以看出，本发明提供的无卤阻燃型树脂组合物在保证具有较高玻璃化转变温度，优良耐湿热性的同时，有效提升了树脂组合物的介电性能和剥离强度稳定性；并使预浸料和覆铜箔层压板具有优异的综合性能。
应该注意到并理解，在不脱离后附的权利要求所要求的本发明的精神和范围的情况下，能够对上述详细描述的本发明做出各种修改和改进。因此，要求保护的技术方案的范围不受所给出的任何特定示范教导的限制。
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. 一种无卤阻燃型树脂组合物，其特征在于，以固体组分重量份计，包括如下组分：
    (A)烷基苯酚环氧树脂：5～80重量份；
    (B)苯并噁嗪树脂：10～80重量份；
    (C)苯乙烯马来酸酐树脂：2～30重量份；
    (D)阻燃剂：1～30重量份；
    (E)酸性填料：0.5～100重量份，其pH值在2～6之间。
  2. 如权利要求1所述的无卤阻燃型树脂组合物，其特征在于，所述烷基苯酚环氧树脂的结构如下所示：
    Figure PCTCN2017078501-appb-100001
    其中，R1，R2独立地为取代或未取代的碳原子数为4～8的直链烷基或支链烷基，优选正丁基或正辛基；n为2～20之间的整数；
    优选地，所述无卤阻燃型树脂组合物中，烷基苯酚环氧树脂的含量为10～35重量份。
  3. 如权利要求1或2所述的无卤阻燃型树脂组合物，其特征在于，所述苯并噁嗪树脂选自双酚A型苯并噁嗪树脂、双环戊二烯型苯并噁嗪树脂、双酚F型苯并噁嗪树脂、酚酞型苯并噁嗪树脂或MDA型苯并噁嗪树脂中的任意一种或至少两种的混合物；
    优选地，所述无卤阻燃型树脂组合物中，苯并噁嗪树脂的含量为30～65重量份。
  4. 如权利要求1-3之一所述的无卤阻燃型树脂组合物，其特征在于，所述苯乙烯马来酸酐树脂中苯乙烯链段单元和马来酸酐链段单元的比例介于8∶1～1∶1之间；
    优选地，所述无卤阻燃型树脂组合物中，苯乙烯马来酸酐树脂的含量为5～20重量份；
    优选地，所述阻燃剂选自间苯二酚-双(磷酸二苯酯)、双酚A-双(磷酸二苯酯)、间苯二酚-双(2，6-二甲苯基磷酸酯)、甲基磷酸二甲酯或磷腈化合物中的任意一种或至少两种的混合物；
    优选地，所述无卤阻燃型树脂组合物中，阻燃剂的含量为3～20重量份。
  5. 如权利要求1-4之一所述的无卤阻燃型树脂组合物，其特征在于，所述酸性填料选自硅微粉、石英粉、云母粉、黏土、草酸钙或炭黑中的任意一种或至少两种的混合物；
    优选地，所述酸性填料的粒径为50nm～50μm；
    优选地，所述酸性填料的pH值为4～6；
    优选地，所述无卤阻燃型树脂组合物中，酸性填料的含量为5～60重量份。
  6. 如权利要求1-5之一所述的无卤阻燃型树脂组合物，其特征在于，所述无卤阻燃型树脂组合物还包括非酸性填料；
    优选地，所述非酸性填料选自碳酸钙、硫酸钙、氧化铝、硫酸钡、陶瓷粉、滑石粉或水滑石中的任意一种或至少两种的混合物；
    优选地，所述非酸性填料的添加量为0～100重量份；
    优选地，所述无卤阻燃型树脂组合物还包括(F)固化促进剂：0.1～1重量 份；
    优选地，所述固化促进剂选自咪唑类促进剂及其衍生物、吡啶类促进剂或路易斯酸类促进剂中的任意一种或至少两种的混合物。
  7. 一种无卤阻燃型树脂组合物的制备方法，其特征在于，所述方法为：
    向所述无卤阻燃型树脂组合物中添加pH值介于2～6的酸性填料；
    所述无卤阻燃型树脂组合物中包括烷基苯酚环氧树脂、苯并噁嗪树脂和苯乙烯马来酸酐树脂。
  8. 一种预浸料，其含有权利要求1-6之一所述的无卤阻燃型树脂组合物或根据权利要求7所述的方法制得的树脂组合物。
  9. 一种层压板，其包括至少1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1张如权利要求8所述的预浸料。
PCT/CN2017/078501 2016-12-30 2017-03-29 一种无卤阻燃型树脂组合物及其制成的预浸料和覆铜箔层压板 WO2018120472A1 (zh)

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JP2021154732A (ja) * 2020-03-25 2021-10-07 日立金属株式会社 軟磁性合金薄帯の積層体の製造方法
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