CN110643131A - Resin composition, and prepreg, laminated board and printed wiring board provided with same - Google Patents

Resin composition, and prepreg, laminated board and printed wiring board provided with same Download PDF

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CN110643131A
CN110643131A CN201910964451.XA CN201910964451A CN110643131A CN 110643131 A CN110643131 A CN 110643131A CN 201910964451 A CN201910964451 A CN 201910964451A CN 110643131 A CN110643131 A CN 110643131A
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phosphorus
parts
styrene
modified
epoxy
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CN110643131B (en
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杨宋
焦锋
崔春梅
陈诚
马建
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Changshu Shengyi Technology Co ltd
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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
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a resin composition, and a prepreg, a laminated board and a printed circuit board with the resin composition. The resin composition includes: hydrocarbon resin, crosslinking assistant and flame retardant; the hydrocarbon resin at least contains epoxy modified hydrocarbon resin; the flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound. According to the resin composition, phosphorus-containing atoms are well introduced into a curing and crosslinking system of the hydrocarbon resin through the reaction of the phosphorus-containing anhydride compound and the epoxy modified hydrocarbon resin, so that the substrate material which simultaneously meets halogen-free flame retardance, low dielectric constant and low dielectric loss value is obtained.

Description

Resin composition, and prepreg, laminated board and printed wiring board provided with same
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a resin composition, and a prepreg, a laminated board and a printed circuit board with the resin composition.
Background
In recent years, with the rapid development of wireless communication technology and electronic products, electronic circuits have come to a stage of high speed information processing and high frequency signal transmission, but when the frequency is higher than 300MHz, even higher than GHz, the electrical properties of the substrate will seriously affect the characteristics of the electronic circuits, and thus the dielectric constant and dielectric loss value of the substrate are required to be higher.
On the other hand, because electronic and electrical equipment have strict requirements on safety and combustion performance, the corresponding printed wiring board for the relevant equipment and prepreg, laminated board and metal foil-clad laminated board also meet the relevant flame-retardant safety requirements. It is conventional practice to use brominated epoxy resins or TBBA or other additive type bromine containing flame retardants. For example, in chinese patent CN101796132B, the flame retardant property is improved by halogen flame retardant to meet the flame retardant requirement. However, such bromine-containing epoxy resins or halogen flame retardants generate harmful substances such as hydrogen halide during combustion, and thus, such flame retardant methods that are harmful to human bodies and the environment have been increasingly focused and controlled. In order to improve the environmental problem, phosphorus-containing flame retardants such as phosphate esters, DOPO, phosphazene or phosphate salts are generally used at present, but it is difficult to select phosphorus-containing flame retardants with good compatibility and reactivity in polyphenylene ether resin systems with poor solubility and compatibility.
Disclosure of Invention
The invention aims to provide a resin composition with low dielectric constant, low dielectric loss, halogen-free flame retardance and high heat resistance, and a prepreg, a laminated board and a printed wiring board prepared by using the resin composition.
In order to achieve the purpose, the invention adopts the following technical scheme:
a resin composition comprising:
a hydrocarbon resin containing at least an epoxy-modified hydrocarbon resin;
a crosslinking aid;
the flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound.
Has the advantages that: according to the resin composition, phosphorus-containing atoms are well introduced into a curing and crosslinking system of the hydrocarbon resin through the reaction of the phosphorus-containing anhydride compound and the epoxy modified hydrocarbon resin, so that the substrate material which simultaneously meets halogen-free flame retardance, low dielectric constant and low dielectric loss value is obtained.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
While the following is a detailed description of the embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
The term "comprising" or "containing" in the present specification means that other components capable of imparting different characteristics to the resin composition may be contained in addition to the components.
"based on 100 parts by weight of the resin composition" in the present specification means that the total amount of components excluding the filler, the catalyst, the auxiliary and the initiator is 100 parts by weight.
The resin composition in the preferred embodiment of the present invention comprises (A) a hydrocarbon resin, (B) a crosslinking assistant, and (C) a flame retardant.
Wherein the hydrocarbon resin contains at least an epoxy-modified hydrocarbon resin.
Specifically, the epoxy modified hydrocarbon resin is at least one selected from epoxy modified polybutadiene, epoxy modified polypentadiene, epoxy modified polyisoprene, epoxy modified styrene-butadiene copolymer, epoxy modified styrene-butadiene-styrene copolymer, epoxy modified hydrogenated diene-butadiene-styrene copolymer and epoxy modified styrene-pentadiene copolymer.
Further, the hydrocarbon resin may contain polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride-diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride-styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, polybutadiene-isoprene copolymer, polybutadiene-butadiene-styrene copolymer, polybutadiene-isoprene copolymer, polybutadiene-, At least one of an ethylene-cyclopentadiene copolymer, a norbornene polymer, and a modified norbornene polymer. "modified" as referred to in this paragraph refers to non-epoxy modifications, that is, modifications of compounds or polymers with any other group than epoxy or epoxy-containing groups, such as hydroxyl, amino or reactive ester group modifications.
In particular, the hydrocarbon resin is selected from at least one of the following mixtures: a mixture of epoxy-modified polybutadiene and polybutadiene, a mixture of epoxy-modified polypentadiene and polypentadiene, a mixture of epoxy-modified polybutadiene and styrene-butadiene copolymer, and a mixture of epoxy-modified polybutadiene and styrene-butadiene-styrene copolymer.
Further preferably, the hydrocarbon resin includes at least one selected from the following structures in addition to the epoxy-modified hydrocarbon resin:
Figure BDA0002230009680000031
(a is an integer of 1 to 60),
(a is an integer of 1 to 60),
Figure BDA0002230009680000033
(a and b are the same or different and are respectively selected from integers of 1-60)(a and b are the same or different and are respectively selected from integers of 1-60)
Figure BDA0002230009680000041
(a, b and c are the same or different and are respectively selected from integers of 1 to 60)
Figure BDA0002230009680000042
(a is an integer of 1 to 60),
(a is an integer of 1 to 60),
Figure BDA0002230009680000044
a is an integer of 1 to 60).
Further, in the styrene-butadiene copolymer, the styrene content is 50 mass% or less, and the butadiene content is 50 mass% or more; preferably, the styrene-butadiene copolymer has a styrene content of 20 to 50% by mass, a butadiene content of 50 to 80% by mass, and a 1, 2-ethylene content of 30 to 70% by mass.
The crosslinking assistant is at least one of triallyl isocyanate monomer (TAIC) or prepolymer thereof, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
Further, the crosslinking aid is preferably TAIC or a prepolymer thereof.
The flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound. Through the reaction of the phosphoric anhydride compound and the epoxy modified hydrocarbon resin, phosphorus-containing atoms are well introduced into a curing crosslinking system of the hydrocarbon resin, and the substrate material which simultaneously meets halogen-free flame retardance, low dielectric constant and low dielectric loss value is obtained.
Specifically, the phosphorus-containing compound (I) has the following structure:
Figure BDA0002230009680000051
X1and X2Are the same or different and are selected from
Figure BDA0002230009680000052
Figure BDA0002230009680000053
Wherein R is11And R12Identical or different, R11And R12Are respectively selected from C1-C5 alkyl, benzoxazine, aromatic phenyl, naphthyl, substituted aromatic phenyl or substituted naphthyl; r1And R2Identical or different, R1And R2Are respectively selected from hydrogen, C1-C5 alkyl, aromatic phenyl, naphthyl, aromatic phenyl containing substituent or naphthyl containing substituent; r3Selected from hydrogen, C1-C5 alkyl groups or siloxy groups.
Further, X in the structural formula of the phosphorus-containing compound (I)1And X2Are all made of
Figure BDA0002230009680000054
Further, R in the structural formula of the phosphorus-containing compound (I)1And R2Are each selected from hydrogen or methyl.
Further, R in the structural formula of the phosphorus-containing compound (I)3Is hydrogen or a siloxy group selected from
Figure BDA0002230009680000055
Wherein n is an integer of 1 to 3.
Further, R3Preferably, it is
Figure BDA0002230009680000061
When it containsPhosphorus compound formula wherein R3When the silicon-oxygen radical is selected, the phosphorus radical and the silicon radical are introduced into a hydrocarbon resin system, so that the silicon-oxygen radical has the synergistic flame retardance of phosphorus and silicon, and the heat resistance, weather resistance, flame retardance, dielectric property and low water absorption of the silicon-oxygen radical are well embodied, and therefore the high-frequency high-speed copper-clad plate can provide excellent dielectric property, humidity resistance and heat resistance required by a high-frequency high-speed copper-clad plate.
In any of the above technical solutions of the flame retardant, the flame retardant further contains other phosphorus-containing compound (II), and the phosphorus-containing compound (II) is selected from phosphazenes, modified phosphazenes, phosphate esters, DOPO-HQ, DOPO-NQ, and mixtures thereof,
Figure BDA0002230009680000062
(m is an integer of 1 to 5),
Figure BDA0002230009680000063
Or DPO.
The DOPO, DOPO-HQ, DOPO-NQ,
Figure BDA0002230009680000065
Respectively, the following structures are shown:
Figure BDA0002230009680000066
preferably, the phosphorus-containing compound (II) is an additive phosphorus-containing compound selected from phosphazenes or modified phosphazenes,
Figure BDA0002230009680000071
When the phosphorus-containing compound (I) and the phosphorus-containing compound (II) are mixed for use, a phosphorus-containing group is properly introduced into a hydrocarbon resin curing system, and on the basis of satisfying halogen-free flame retardance, the radical curing crosslinking reaction of the hydrocarbon resin is not hindered, so that a substrate material for high frequency and high speed having halogen-free flame retardance, high heat resistance, low dielectric constant and low dielectric loss can be obtained.
When the phosphorus-containing compound (I) and the phosphorus-containing compound (II) are mixed for use, the weight ratio thereof is (1-50): (1-30). For example, the weight ratio of the phosphorus compound (I) to the phosphorus-containing compound (II) is: 50:30.
Any one of the above-mentioned hydrocarbon resin, any one of the above-mentioned crosslinking assistant, and any one of the above-mentioned flame retardant may be combined with each other to constitute the resin composition.
In addition, the resin composition comprises the following components in percentage by weight:
(A) hydrocarbon resin: 20-150 parts by weight;
(B) crosslinking assistant agent: 1-80 parts by weight;
(C) flame retardant: 1-60 parts by weight;
as a further preferred of the present invention, the resin composition comprises, by weight:
(A) polybutadiene: 30-70 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene;
(B) TAIC: 2-50 parts by weight;
(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;
as a further preferred of the present invention, the resin composition comprises, by weight:
(A) styrene-butadiene copolymer: 30-60 parts by weight of epoxy modified polybutadiene, wherein the weight of the epoxy modified polybutadiene is 20-70 parts by weight;
(B) TAIC: 2-50 parts by weight;
(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;
as a further preferred of the present invention, the resin composition comprises, by weight:
(A) styrene-butadiene-styrene copolymer: 30-50 parts by weight of epoxy modified polybutadiene, wherein the weight of the epoxy modified polybutadiene is 20-70 parts by weight;
(B) TAIC: 2-50 parts by weight;
(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;
as a further preferred of the present invention, the resin composition comprises, by weight:
(A) styrene-butadiene-styrene copolymer: 30-50 parts by weight of epoxy modified polyisoprene, wherein 20-70 parts by weight of epoxy modified polyisoprene;
(B) TAIC: 2-50 parts by weight;
(C) phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;
the resin composition may further include a filler in an amount of 0 to 200 parts by weight based on 100 parts by weight of the resin composition, based on any one of the above resin compositions, and it is understood that the resin composition may or may not include the filler.
For example, the filler content is 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight, 120 parts by weight, 130 parts by weight, 140 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, or 200 parts by weight; and the particular points between the above numerical values, are not intended to be exhaustive or to be in a concise sense and the invention is not intended to be exhaustive of the particular points included in the range.
Preferably, the filler content is 10 to 100 parts by weight, more preferably 30 to 70 parts by weight.
Specifically, the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
More preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Preferably, the filler is silica, more preferably, surface-treated spherical silica.
Preferably, the filler has a median particle size of 1 to 15 μm, such as 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and specific values therebetween are not intended to be exhaustive, and for brevity, the invention is not intended to be limited to the specific values included in the ranges.
More preferably, the median value of the particle size of the filler is 1-10 μm.
Specifically, the surface treatment agent for treating the silica is a silane coupling agent such as an epoxy silane coupling agent or an aminosilane coupling agent.
The resin composition may further include a curing accelerator based on any one of the resin compositions described above.
Preferably, the curing accelerator is selected from at least one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, and zinc isooctoate, for example: a mixture of 4-dimethylaminopyridine and 2-methylimidazole, a mixture of 2-methylimidazole and 2-methyl-4-ethylimidazole, a mixture of 2-phenylimidazole and zinc isooctoate, and a mixture of 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole, although not limited thereto.
The curing accelerator is contained in an amount of 0.001 to 5 parts by weight, for example, 0.001 part by weight, 0.01 part by weight, 1 part by weight, 2.5 parts by weight, 5 parts by weight, and specific points between the above-mentioned values, based on 100 parts by weight of the resin composition, are limited to space and in the interest of brevity, and the present invention is not exhaustive of the specific points included in the range.
More preferably, the curing accelerator is contained in an amount of 0.01 to 1 part by weight.
The resin composition may further include an initiator based on any one of the above resin compositions in terms of reactivity between resin components; the initiator is 0.001 to 6 parts by weight based on 100 parts by weight of the resin composition; the initiator can be selected from azo initiators, peroxy initiators and redox initiators, and preferably one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile.
Based on any one of the resin compositions, according to different requirements of final products, the resin composition further comprises other auxiliary agents, and preferably, the other auxiliary agents are 0-5 parts by weight based on 100 parts by weight of the resin composition.
The other auxiliary agents comprise at least one of a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is amino silane compound having amino group and having hydrolytic group or hydroxyl group such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, epoxy silane compound having epoxy group and having hydrolytic group or hydroxyl group such as 3-acryloxypropyltrimethoxysilane, vinyl silane compound having vinyl group and having hydrolytic group or hydroxyl group such as gamma-methacryloxypropyltrimethoxysilane, and cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all product names) manufactured by BYK; the dye is fluorescent dye and black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), pyridine complex, azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
The organic solvent and the solvent used in the present invention are not particularly limited. For example, the organic solvent may be selected from one or a combination of any of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene and cyclohexane.
The amount of the solvent to be added is selected by a person skilled in the art according to his own experience, as long as the viscosity of the resulting glue solution is such that it is suitable for use.
The invention also provides a prepreg, which comprises a reinforcing material and the resin composition attached to the surface of the reinforcing material.
The reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth.
In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (3) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-10min at the temperature of 50-170 ℃, and drying to obtain the prepreg.
The invention also provides a laminated board which comprises at least one prepreg and the metal foil formed on at least one surface of the prepreg.
The laminated board is formed by bonding one or two prepregs together by heating and pressing, and then bonding a metal foil on one side or two sides of the laminated board by heating and pressing.
The preparation steps of the laminated board are as follows: and coating a metal foil on one side or both sides of one prepreg, or coating a metal foil on one side or both sides of at least 2 prepregs after laminating, and carrying out hot press forming to obtain the laminated board.
The pressing condition of the laminated board is that the laminated board is pressed for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.
In order to achieve the above object, the present invention further provides a printed wiring board, which includes at least one prepreg as described above, or at least one laminate as described above.
Compared with the prior art, the invention has the following advantages:
according to the invention, through the reaction of the acid anhydride group in the phosphorus-containing compound and the epoxy group in the hydrocarbon resin, the phosphorus-containing group is well introduced into a hydrocarbon resin curing crosslinking system, and no secondary hydroxyl is generated in the reaction process of the acid anhydride group and the epoxy group, so that the low dielectric constant and low dielectric loss of the hydrocarbon resin are not reduced, and simultaneously, the dielectric constant and dielectric loss value of a cured product are further reduced by matching with other hydrocarbon resins, so that the requirements of the field of the current 5G communication electronic substrate are well met;
when R in the structure of the phosphorus-containing compound (I)3When the silicon-oxygen base is selected, the phosphorus group and the silicon group are introduced into a hydrocarbon resin system, so that the silicon-oxygen base has the synergistic flame retardance of phosphorus and silicon, and the heat resistance, weather resistance, flame retardance, dielectric property and low water absorption of the silicon-oxygen base are well embodied, and therefore the high-frequency high-speed copper-clad plate can provide excellent dielectric property, humidity resistance and heat resistance required by the high-frequency high-speed copper-clad plate;
when the phosphorus-containing compound (I) and the phosphorus-containing compound (II) are mixed for use, a phosphorus-containing group is properly introduced into a hydrocarbon curing system, the compatibility and reactivity between hydrocarbon resin and other resins are not influenced, and the curing crosslinking reaction of the hydrocarbon resin is not hindered on the basis of meeting halogen-free flame retardance, so that the high-frequency high-speed substrate material with halogen-free flame retardance, high heat resistance, low dielectric constant and low dielectric loss can be obtained.
The following examples are provided to further illustrate embodiments of the present invention. It is to be understood that the embodiments of the present invention are not limited to the following specific examples. The present invention can be modified as appropriate without changing the scope of the claims.
Synthesis example 1: synthesis of phosphorus-containing Compound (I)
Nadic anhydride
Figure BDA0002230009680000121
And phosphorus compounds
Figure BDA0002230009680000122
The reaction is carried out in the presence of an initiator benzoyl peroxide, the reaction temperature is 135 ℃, and carbon-carbon double bonds in nadic anhydride are reacted with active hydrogen groups in a phosphorus compound to obtain a phosphorus-containing compound (I) with the following structure A.
Synthesis example 2: synthesis of phosphorus-containing Compound (I)
Mixing internal methyl nadic anhydride
Figure BDA0002230009680000124
And phosphorus compounds
Figure BDA0002230009680000125
The reaction is carried out in the presence of an initiator benzoyl peroxide, the reaction temperature is 135 ℃, and carbon-carbon double bonds in nadic anhydride are reacted with active hydrogen groups in a phosphorus compound to obtain a phosphorus-containing compound (I) with the following structure B.
Figure BDA0002230009680000126
Synthesis example 3: synthesis of phosphorus-containing Compound (I)
Nadic anhydride
Figure BDA0002230009680000131
And phosphorus compounds
Figure BDA0002230009680000132
Reacting in the presence of initiator benzoyl peroxide at 135 deg.c to react the carbon-carbon double bond in nadic anhydride with active hydrogen in phosphorus compoundThe following phosphorus-containing compound (I) of structure C is obtained.
Figure BDA0002230009680000133
Synthesis example 4: synthesis of phosphorus-containing Compound (I)
Mixing silicon-oxygen-containing nadic anhydride
Figure BDA0002230009680000134
And phosphorus compounds
Figure BDA0002230009680000135
The reaction is carried out in the presence of an initiator benzoyl peroxide, the reaction temperature is 135 ℃, and carbon-carbon double bonds in nadic anhydride are reacted with active hydrogen groups in a phosphorus compound to obtain a phosphorus-containing compound (I) with the following structure D.
Figure BDA0002230009680000136
The components and contents of the resin compositions of examples 1 to 7 and comparative examples 1 to 3 are shown in the following table 1:
TABLE 1
Figure BDA0002230009680000141
The detailed specification of the components is as follows:
TABLE 2
Figure BDA0002230009680000142
Figure BDA0002230009680000151
The laminate properties obtained are shown in table 3.
TABLE 3
Figure BDA0002230009680000152
The performance evaluation method comprises the following steps:
(1) glass transition temperature (Tg): using DMA test, DMA as specified by IPC-TM-6502.4.24.4
Test methods were performed.
(2) Dielectric constant and dielectric dissipation factor: testing was carried out according to the IPC-TM-6502.5.5.9 method
The rate is 1 GHz.
(3) Flame retardancy: the flammability was measured according to the UL94 protocol.
(4) Peel strength: the test was carried out according to IPC-TM-6502.4.8.
(5) Water absorption: the water absorption was measured according to the water absorption method defined in IPC-TM-602.6.2.1.
As can be seen from the above Table 3, examples 1 to 5 obtained a flame retardant having excellent V-0 rating without halogen, low dielectric constant, low dielectric loss, high heat resistance, low water absorption and high peel strength simultaneously as shown in the above Table 3. The example 4 in which the phosphorus-containing compound having a siloxy group was used had a higher Tg and a lower water absorption than the other examples, while the dielectric constant and the dielectric loss value were not decreased; furthermore, compared with the comparative example adopting the additive phosphazene flame retardant, the Tg value is reduced, and the dielectric constant and the dielectric loss value are increased; further, in comparative example 3 using a large amount of phosphorus-containing compound, although the halogen-free flame retardancy satisfies V-0 class, the water absorption rate is remarkably increased due to a large amount of phosphorus.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above list of details is only for the concrete description of the feasible embodiments of the present application, they are not intended to limit the scope of the present application, and all equivalent embodiments or modifications that do not depart from the technical spirit of the present application are intended to be included within the scope of the present application.

Claims (13)

1. A resin composition, comprising:
a hydrocarbon resin containing at least an epoxy-modified hydrocarbon resin;
a crosslinking aid;
the flame retardant at least contains a phosphorus-containing compound (I), and the phosphorus-containing compound (I) is a phosphorus-containing anhydride compound.
2. The resin composition according to claim 1, wherein the epoxy-modified hydrocarbon resin is at least one selected from the group consisting of epoxy-modified polybutadiene, epoxy-modified polypentadiene, epoxy-modified polyisoprene, epoxy-modified styrene-butadiene copolymer, epoxy-modified styrene-butadiene-styrene copolymer, epoxy-modified hydrogenated diene-butadiene-styrene copolymer, and epoxy-modified styrene-pentadiene copolymer.
3. The resin composition of claim 1, wherein the hydrocarbon resin further comprises polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleic anhydride-diene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleic anhydride-styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, polyisoprene, polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-styrene copolymer, isoprene copolymer, styrene-butadiene, At least one of butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, modified norbornene polymer.
4. The resin composition according to claim 1, wherein the hydrocarbon resin is selected from at least one of the following mixtures: a mixture of epoxy-modified polybutadiene and polybutadiene, a mixture of epoxy-modified polypentadiene and polypentadiene, a mixture of epoxy-modified polybutadiene and styrene-butadiene copolymer, and a mixture of epoxy-modified polybutadiene and styrene-butadiene-styrene copolymer.
5. The resin composition according to any one of claims 1 to 4, wherein the phosphorus-containing compound (I) has the following structure:
Figure FDA0002230009670000021
X1and X2Are the same or different, X1And X2Are respectively selected from
Figure FDA0002230009670000023
Wherein R is11And R12Identical or different, R11And R12Are respectively selected from C1-C5 alkyl, benzoxazine, aromatic phenyl, naphthyl, substituted aromatic phenyl or substituted naphthyl; r1And R2Identical or different, R1And R2Are respectively selected from hydrogen, C1-C5 alkyl, aromatic phenyl, naphthyl, aromatic phenyl containing substituent or naphthyl containing substituent; r3Selected from hydrogen, C1-C5 alkyl groups or siloxy groups.
6. The resin composition according to claim 5, wherein R in the structural formula of the phosphorus-containing compound (I)3Is a siloxy group selected from
Wherein n is an integer of 1 to 3.
7. The resin composition as claimed in claim 5, wherein the flame retardant further comprises a phosphorus-containing compound (II) selected from phosphazenes, modified phosphazenes, phosphoric acid esters, DOPO-HQ, DOPO-NQ, phosphorus-containing compounds, phosphorus-,
Figure FDA0002230009670000025
(m is an integer of 1 to 5),Or DPO, wherein the weight ratio of the phosphorus-containing compound (I) to the phosphorus-containing compound (II) is (1-50): (1-30).
8. The resin composition as claimed in claim 1, wherein the resin composition comprises the following components in percentage by weight: 20-150 parts by weight; crosslinking assistant agent: 1-80 parts by weight; flame retardant: 1-60 parts by weight.
9. The resin composition according to claim 1,
the resin composition includes polybutadiene: 30-70 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene; TAIC: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts.
Or, the resin composition comprises a styrene-butadiene copolymer: 30-60 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene; triallyl isocyanate monomer: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;
or, the resin composition comprises a styrene-butadiene-styrene copolymer: 30-50 parts of epoxy modified polybutadiene, 20-70 parts of epoxy modified polybutadiene; triallyl isocyanate monomer: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts;
or, the resin composition comprises a styrene-butadiene-styrene copolymer: 30-50 parts of epoxy modified polyisoprene, 20-70 parts of epoxy modified polyisoprene; triallyl isocyanate monomer: 2-50 parts by weight; phosphorus-containing compound (I): 1-30 parts by weight; phosphorus-containing compound (II): 1-15 parts.
10. The resin composition of claim 1, wherein the crosslinking coagent is at least one of a triallyl isocyanate monomer, a triallyl isocyanate monomer prepolymer, a butadiene monomer, a styrene monomer, a pentadiene monomer, a norbornene monomer, or a cyclopentadiene monomer.
11. A prepreg characterized in that: a resin composition comprising a reinforcing material and impregnated in the reinforcing material, the resin composition being as defined in any one of claims 1 to 10.
12. A laminate, characterized by: comprising at least one prepreg according to claim 11, a metal foil being formed on at least one side of the prepreg.
13. A printed wiring board characterized in that: the printed wiring board comprises at least one prepreg according to claim 11, or at least one laminate according to claim 12.
CN201910964451.XA 2019-10-11 2019-10-11 Resin composition, and prepreg, laminated board and printed wiring board provided with same Active CN110643131B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289545A (en) * 2007-04-18 2008-10-22 日立化成工业株式会社 Prepreg, multilayer printed wiring board and electronic parts using the same
CN103289283A (en) * 2013-06-08 2013-09-11 苏州生益科技有限公司 Thermosetting resin composition, as well as prepreg and laminated board manufactured by using same
WO2019090563A1 (en) * 2017-11-09 2019-05-16 Blue Cube Ip Llc Phosphorated anhydride containing epoxy resin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289545A (en) * 2007-04-18 2008-10-22 日立化成工业株式会社 Prepreg, multilayer printed wiring board and electronic parts using the same
CN103289283A (en) * 2013-06-08 2013-09-11 苏州生益科技有限公司 Thermosetting resin composition, as well as prepreg and laminated board manufactured by using same
WO2019090563A1 (en) * 2017-11-09 2019-05-16 Blue Cube Ip Llc Phosphorated anhydride containing epoxy resin

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