CN109354827A - It is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board - Google Patents

It is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board Download PDF

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Publication number
CN109354827A
CN109354827A CN201811160788.7A CN201811160788A CN109354827A CN 109354827 A CN109354827 A CN 109354827A CN 201811160788 A CN201811160788 A CN 201811160788A CN 109354827 A CN109354827 A CN 109354827A
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resin
parts
combination
halogen
epoxy resin
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CN201811160788.7A
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CN109354827B (en
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张龙
霍国洋
李莎
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SHAANXI SHENGYI SCI TECH Co Ltd
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SHAANXI SHENGYI SCI TECH 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
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of 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
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/02—Layered products comprising a layer of paper or cardboard next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/028—Paper layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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

Abstract

The present invention provide it is a kind of have halogen without antimony resin combination, using its prepreg, laminate and printed circuit board, it is described that have halogen include the component of following parts by weight: 20 parts~50 parts phosphorous epoxy resins, 20 parts~50 parts non-flame resistant type epoxy resin, 20 parts~60 parts composite curing agents, 0.05 part~1.0 parts curing accelerators and 10 parts~50 parts compounded mixs without antimony resin combination；The compounded mix is the combination of phosphorous flame-retardant material and nitrogen series anti-flaming material, and the composite curing agent is the composite curing agent containing halogen.The present invention makes resin composition system achieve the effect that the bromo- phosphorus-nitrogen coordinated fire-retardant of phosphorus-using compounded mix and composite curing agent, limitation requirement of the international environment regulation to antimonial is reached, and resin combination of the present invention can also make its solidfied material have the advantages such as good heat resistance and resistance to dip solderability and lower water absorption rate.

Description

It is a kind of to have halogen without antimony resin combination, is electric using its prepreg, laminate and printing Road plate
Technical field
The invention belongs to technical field of laminates, it is related to a kind of having halogen without antimony resin combination, the prepreg using it, layer Pressing plate and printed circuit board.
Background technique
CEM-1 copper-clad laminate be using electronic-grade glass fiber cloth and bleached wood pulp paper as reinforcing material, be soaked respectively with Fabric and core material is made in copper-clad laminate resin combination, and coated with copper foil, forms through hot pressing.Anti-flammability is that CEM-1 covers The primary performance that copper-clad laminate must reach, but CEM-1 copper-clad laminate is the wood pulp paper using wood pulp paper bonding sheet as core material Itself is flammable, to guarantee other performances of CEM-1 copper-clad laminate, the especially performances such as heat resistance, toughness, moisture resistance Under the premise of, the anti-flammability for improving CEM-1 copper-clad laminate is difficult.Currently, there is the fire-retardant of halogen CEM-1 copper-clad laminate Property relies primarily on halogen antimony synergistic flame-retardant system and is achieved.
CN103804819A discloses one kind without antimony flame retardant composite material, while being related to a kind of gathering for not antimony containing compounds Vinyl chloride resin composition, it is environmentally protective, and the balance for realizing anti-flammability, heat resistance, cold resistance and electrical insulating property is excellent It is different.The flame retarding function of this scheme mainly passes through addition montmorillonite, hydrotalcite, magnalium flame retardant, silicone flame retardant, nitrogen phosphorus Flame retardant, phosphate ester flame retardants are achieved, while being added to a large amount of nanon calcium carbonatefilled agent, and calcium carbonate acid and alkali-resistance Property is poor, will affect the processability in plate later period in copper-clad laminate.In addition, the patent is primarily related to engineering thermoplastic Cable in plastics cable material field, it is little with copper-clad laminate (thermosetting material) technical field correlation.
CN103764739A disclose by by the polyphenylene ether flame retardant of a kind of fluoropolymer resin, certain halogenations and A kind of non-brominated phenoxy group oligomer or combination of polymers prepare the flame-retardant polymer of no antimony, this quasi polymer has excellent Anti-flammability and excellent physical characteristic.But the patent is primarily related to thermoplastic technical field, with copper foil covered pressure Plate (thermosetting material) technical field correlation is little.
CN 101974206A discloses a kind of composition epoxy resin, is made of the raw material of following weight proportion: containing connection The epoxy resin 5~30 of benzene structural unit；Phenol-formaldehyde resin modified 5~20；Inorganic filler 50~300；Curing accelerator 0.5~ 2.5；Silane coupling agent 0.5~4.5；Colorant 0.1~5；Release agent 0.5~4.5.The invention composition epoxy resin can not only The flame-retardant standard for reaching UL-94V-0 grades is a kind of resin combination of halogen-free stibium-free, however it is suitable for semiconductor devices And integrated circuit, there is no be applied to copper-clad laminate.
There is halogen without antimony CEM-1 copper-clad laminate therefore, it is necessary to developing one kind and meets international newest environmental legislation pair The environmental requirement of electronic product.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind to have halogen without antimony resin combination, uses it Prepreg, laminate and printed circuit board.
To achieve this purpose, the present invention adopts the following technical scheme:
On the one hand, the present invention, which provides one kind, has halogen without antimony resin combination, described to have halogen without antimony resin combination including such as The component of lower parts by weight:
20 parts~50 parts phosphorous epoxy resins, 20 parts~50 parts non-flame resistant type epoxy resin, 20 parts~60 parts composite curings Agent, 0.05 part~1.0 parts curing accelerators and 10 parts~50 parts compounded mixs；The compounded mix is phosphorous flame-retardant material and nitrogen The combination of series flame retardant material, the composite curing agent are the composite curing agent containing halogen.
In the present invention, bromo- by making resin composition system reach phosphorus-using compounded mix and composite curing agent The effect of phosphorus-nitrogen coordinated fire-retardant, having broken tradition has halogen antimony cooperative flame retardant system in halogen CEM-1 copper-clad laminate that can not be substituted Technical bottleneck, halogen antimony composite flame retardant system is converted into no antimony composite flame retardant system, halogen CEM-1 has been completely removed and has covered copper Antimony containing compounds in foil laminate have reached limitation requirement of the international environment regulation to antimonial, and of the present invention Resin composition system can also have the advantages such as good heat resistance and resistance to dip solderability and lower water absorption rate.
There is halogen without in antimony resin combination in of the invention, the content of the phosphorous epoxy resin is 20 parts by weight, 23 weights Measure part, 25 parts by weight, 28 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 43 parts by weight, 45 parts by weight, 48 parts by weight or 50 parts by weight.
Preferably, in the phosphorous epoxy resin phosphorus content be 2%~4%, such as 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.3%, 3.5%, 3.8% or 4%.
The phosphorus content of phosphorous epoxy resin is too low in the present invention will affect anti-flammability；Phosphorus content is too high, and resin reaction is living Property reduce, will affect the crosslink density of solidfied material, and then influence the heat resistance of solidfied material.
Preferably, the phosphorous epoxy resin is DOPO base epoxy, ODOPB base epoxy, three phosphonitrile basic ring of ring In oxygen resin or diphenyl phosphine oxide epoxy resin any one or at least two combination.
There is halogen without in antimony resin combination in of the invention, the content of the non-flame resistant type epoxy resin can be 20 weight Part, 23 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 33 parts by weight, 35 parts by weight, 38 parts by weight, 40 parts by weight, 43 Parts by weight, 45 parts by weight, 48 parts by weight or 50 parts by weight.
Non-flame resistant type epoxy resin in the present invention is the higher polyfunctional epoxy resin of reactivity, in resin combination Main function in object is to improve solidfied material molecular backbone rigidity and crosslink density, the final heat resistance for improving solidfied material.If its Dosage is very few, can not just effectively improve the heat resistance of solidfied material；If its dosage is excessive, it will lead to the increase of solidfied material brittleness, glue Conjunction property reduces.
Preferably, the degree of functionality of the non-flame resistant type epoxy resin is 2~4, such as 2,3 or 4.
Preferably, the non-flame resistant type epoxy resin is bisphenol A type epoxy resin (such as bisphenol A-type epoxy novolac tree Rouge), bisphenol f type epoxy resin, biphenyl type epoxy resin, tris phenol type epoxy, alkyl phenol epoxy resin, dicyclopentadiene ring Oxygen resin, o-cresol type novolac epoxy resin, phenol type novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin Any one or at least two combination.
Preferably, the epoxide equivalent of the non-flame resistant type epoxy resin is 100g/eq~800g/eq, such as such as 100g/ eq、130g/eq、150g/eq、180g/eq、200g/eq、230g/eq、250g/eq、280g/eq、300g/eq、350g/eq、 400g/eq, 450g/eq, 500g/eq, 550g/eq, 600g/eq, 650g/eq, 700g/eq, 750g/eq or 800g/eq.It is preferred that 100g/eq~300g/eq.
In the present invention, the non-flame resistant type epoxy resin refers in particular to the epoxy resin without containing phosphorus, bromine or nitrogen.
Preferably, the composite curing agent is in terms of 100%, including following weight percentage components by its total weight: 25%~55% (such as 25%, 28%, 30%, 33%, 35%, 38%, 40%, 43%, 45%, 48%, 50%, 53% or 55%) plant oil modified phenol-formaldehyde resin, 15%~50% (such as 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45% or bromination phenolic compound 50%) and 10%~40% (such as 10%, 13%, 15%, 18%, 20%, 25%, 28%, 30%, 33%, 35%, 38% or linear phenolic resin 40%).
Preferably, the equivalent of the reactive group to react in the composite curing agent with epoxy group is 100~700g/ Eq, such as 100g/eq, 120g/eq, 150g/eq, 180g/eq, 200g/eq, 230g/eq, 250g/eq, 280g/eq, 300g/ Eq, 350g/eq, 400g/eq, 450g/eq, 500g/eq, 550g/eq, 600g/eq, 650g/eq or 700g/eq.
It is particularly preferred that the equivalent of the plant oil modified phenol-formaldehyde resin be 400~550g/eq (such as 400g/eq, 430g/eq, 450g/eq, 480g/eq, 500g/eq, 520g/eq or 550g/eq), the equivalent of the bromination phenolic compound is 200~300g/eq (such as 200g/eq, 220g/eq, 250g/eq, 280g/eq or 300g/eq), the linear phenolic resin Equivalent is 100~250g/eq (such as 100g/eq, 120g/eq, 150g/eq, 180g/eq, 200g/eq, 220g/eq or 250g/ eq)。
Preferably, the plant oil modified phenol-formaldehyde resin is tung oil modified phenolic resin, epoxidized soybean oil modified phenolic resin In rouge, Cardanol Modified PF Resin, modification of flax oil phenolic resin or castor oil modified phenolic resin any one or extremely Few two kinds of combination.
Preferably, the bromine content of the bromination phenolic compound be 19%~58%, such as 19%, 24%, 28%, 30%, 35%, 38%, 40%, 43%, 45%, 48%, 50%, 55% or 58%, preferably 48%~58%.
The bromine content of bromination phenolic compound is too low in the present invention will affect anti-flammability；Bromine content is too high, and reactivity is living Property reduce, will affect the crosslink density of solidfied material, and then influence the heat resistance of solidfied material；Meanwhile bromine content is too high can be to resin It is influenced with the bonding force of copper foil and reinforcing material.
Preferably, the bromination phenolic compound be tetrabromobisphenol A, tribromphenol or bromination phenolic aldehyde in any one or The combination of person at least two.
Preferably, the linear phenolic resin is phenol type phenolic resin, bisphenol A type phenolic resin, o-cresol type phenolic aldehyde Any one in resin, triphenol phenolic resin, naphthalene type phenolic resin, biphenyl type phenolic resin or dicyclopentadiene phenolic resin Or at least two combination.
The use of composite curing agent in the present invention can effectively improve anti-flammability, the resistance to dip solderability, heat resistance of solidfied material, It also contributes to reducing water absorption rate, improves flexibility.And it can cooperate with compounded mix, reach cooperative flame retardant effect.
In the present invention, three kinds of components of composite curing agent cooperate, and mutually cooperate with, indivisible；Between each component It is cooperateed with each other in terms of anti-flammability, heat resistance, flexibility and solidification process.It is plant oil modified due to containing in composite curing agent Phenolic resin, therefore can effectively improve the toughness of solidfied material, be conducive to the punching processing in plate later period；Due to containing bromination Phenolic compound participates in also providing a large amount of bromo element while curing reaction, is conducive to the anti-flammability for improving solidfied material； Due to containing linear phenolic resin, reactivity is high, water absorption rate is low, is conducive to the heat resistance and wet-heat resisting that improve solidfied material Property.
In the present invention, in the compounded mix weight ratio of phosphorous flame-retardant material and nitrogen series anti-flaming material be (0.8~ 1.2): (1.8~2.2), such as 0.8:1.8,0.8:1.9,0.8:2.0,0.8:2.1,0.8:2.2,0.9:1.9,0.9:2.0, 0.9:2.1、0.9:2.2、1.0:1.8、1.0:1.9、1.0:2.0、1.0:2.1、1.0:2.2、1.1:1.8、1.1:1.9、1.1: 2.0,1.1:2.1,1.2:1.8,1.2:1.9,1.2:2.0,1.2:2.1,1.2:2.2 etc..
Compounded mix with above range weight ratio can effectively improve the anti-flammability, resistance to dip solderability, heat-resisting of solidfied material Property, also available relatively low water absorption rate.
In the present invention, the phosphorus flame retardant in compounded mix decomposes the non-ignitibility liquid film for generating phosphoric acid in burning, Its boiling point is up to 300 DEG C or more.Meanwhile phosphoric acid is further dehydrated and generates metaphosphoric acid, it is poly- inclined that metaphosphoric acid further polymerize generation Phosphoric acid.In this process, blanketing effect is not only played by the coating that phosphoric acid generates, but also since the poly-metaphosphoric acid of generation is Strong acid is very strong dehydrating agent, so that polymer is dehydrated and is carbonized, changes the mode of polymer combustion process and in its surface shape At carbon film to completely cut off air, to play stronger flame retardant effect.In general, phosphorus flame retardant imitates the effect of oxygen-containing polymers Fruit is best, especially applies the significant effect in epoxy-resin systems.
Nitrogenated flame retardant in compounded mix of the invention decomposites CO in burning2、NH3、N2、NOx、H2The gas such as O Body, these are all fire retardant gas, so that the concentration of oxygen in the imflammable gas and air released by pyrolysis is diluted, Achieve the purpose that fire-retardant；In addition polymeric matrix is in burning, it may occur that multiple chemical reaction will form on the surface of matrix One expansion carbon foams layer, it can completely cut off heat transfer, and oxygen is prevented to spread to polymeric inner, effectively prevent the heat of polymer Degradation reaction, and internal volatile fuel is inhibited to escape, to interrupt polymer combustion.
The present invention uses the compounded mix, has played the synergistic effect of phosphorus flame retardant and nitrogenated flame retardant well, And it can be carried out between composite curing agent and phosphorous epoxy resin containing halogen good fit, reach phosphorus-nitrogen-bromine association With fire-retardant purpose.
Preferably, the phosphorous flame-retardant material is dimethyl hypo-aluminum orthophosphate, second diyl zinc hypophosphite, ammonium polyphosphate, diethyl Base hypo-aluminum orthophosphate, dimethyl zinc hypophosphite, aminomethyl phenyl hypo-aluminum orthophosphate, aminomethyl phenyl zinc hypophosphite, hydroxymethyl phenyl hypophosphorous acid Aluminium, polyphenylene phosphoric acid diphenyl sulphone (DPS) ester, diethyl zinc hypophosphite, second diyl hypo-aluminum orthophosphate, appointing in hydroxymethyl phenyl zinc hypophosphite It anticipates a kind of or at least two combinations；Further preferred diethyl hypo-aluminum orthophosphate.
Preferably, the nitrogen series anti-flaming material is cyanurate, melamine phosphate, melamine borate salt, three Poly cyanamid cyanurate, melamine pyrophosphate, melamine polyphosphate, in phosphonitrile any one or at least two Combination, further preferred melamine cyanurate.
Preferably, the average grain diameter of the compounded mix is 1~5 μm, such as 1 μm, 1.3 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm.
Have halogen without in antimony resin combination of the invention, the content of the curing accelerator can for 0.05 parts by weight, 0.08 parts by weight, 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 weight Measure part, 0.8 parts by weight, 0.9 parts by weight or 1 parts by weight.
Preferably, the curing accelerator is tertiary amine, three-level phosphine, metal-organic complex, quaternary ammonium salt or imidazoles Close object in any one or at least two combination.
Preferably, the glyoxaline compound is 2-methylimidazole, -4 methylimidazole of 2- ethyl, 2- phenylimidazole, 2- benzene In -4 methylimidazole of base or 1- 1-cyanoethyl-2-methylimidazole any one or at least two mixture.
In the present invention, curing accelerator additive amount should not be excessive, will excessively will lead to the reaction of epoxy resin component Fastly, by-product can be excessive, and the reduced performance of cured product, craftsmanship is deteriorated；If curing accelerator dosage it is very few, if reacted Slowly, it is unfavorable for the production of prepreg, should ensure that the gelation time of glue should be 100~300s.
On the other hand, the present invention provides a kind of resin adhesive liquid, and the resin adhesive liquid is that have halogen without antimony tree as described above Oil/fat composition is dissolved or dispersed in solvent and obtains.
Preferably, the solvent is the solvent that boiling point is 50 DEG C~180 DEG C.The boiling point and paper base bonding sheet half of the solvent Solidification processing temperature matches, meet the semi-solid preparation stage except solvent requirement, meanwhile, solvent meet to the impregnability of paper base and with The compatibility of resin.
Preferably, the solvent be methanol, ethyl alcohol, acetone, butanone, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate or In cyclohexanone any one or at least two mixing.
Preferably, the solid content of the resin adhesive liquid is 60%~80%, particularly preferred 65%~75%, has the range The impregnability to reinforcing material, available half with high uniformity resin layer thickness can be improved in the resin adhesive liquid of solid content Cured sheets.
On the other hand, the present invention provides a kind of prepreg, after the prepreg includes reinforcing material and passes through impregnation drying Attachment thereon as described above have halogen without antimony resin combination.
Preferably, the reinforcing material is wood pulp paper or rag paper.
On the other hand, the present invention provides a kind of laminate, and the laminate includes an at least prepreg as described above.
On the other hand, the present invention provides a kind of metal-clad laminate, and the metal-clad laminate contains at least one The metal foil of prepreg as described above and the prepreg one or both sides being overlying on after overlapping.
On the other hand, the present invention provides a kind of printed circuit board, and the printed circuit board includes laminate as described above Or metal-clad laminate.
Compared with the existing technology, the invention has the following advantages:
(1) present invention using compounded mix and composite curing agent by making resin composition system reach the bromo- nitrogen of phosphorus- The fire-retardant effect of synergistic, having broken tradition has in halogen CEM-1 copper-clad laminate that halogen antimony cooperative flame retardant system can not be substituted Halogen antimony composite flame retardant system is converted into no antimony composite flame retardant system, has completely removed halogen CEM-1 and covered copper foil by technical bottleneck Antimony containing compounds in laminate have reached limitation requirement of the international environment regulation to antimonial, and of the present invention Resin composition system can also have the advantages such as good heat resistance and resistance to dip solderability and lower water absorption rate.
(2) the CEM-1 copper-clad laminate being prepared using resin combination of the invention, anti-flammability have reached halogen The peer of antimony collaboration system is horizontal, the V-0 grade standard in UL-94, meanwhile, 288 DEG C of thermal stress are increased to 140~148s, with For halogen antimony collaboration system compared to improving 36~39%, water absorption rate is reduced to 0.07~0.09%, drops compared with halogen antimony collaboration system Low 25~41%；T260 is increased to 50~56min, improves 36~42% compared with halogen antimony collaboration system.Thus, this has halogen For no antimony CEM-1 copper-clad laminate while guaranteeing fire-retardant, the comprehensive performances outstanding such as high heat resistance, high wet-heat resisting of also having are excellent Gesture.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright , the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Examples 1 to 6 and comparative example 1~13
The concrete component and constituent content (in parts by weight) of the resin combination of Examples 1 to 6 and comparative example 1~13 are such as Shown in Tables 1 and 2.
The concrete component and constituent content of 1 Examples 1 to 8 resin combination of table
The concrete component and constituent content of 2 comparative example of table, 1~13 resin combination
Each component code name and its corresponding ingredient names are as follows in Tables 1 and 2:
A: phosphorous epoxy resin:
The DOPO base epoxy that A-1 phosphorus content is 3%；
The ODOPB base epoxy that A-2 phosphorus content is 2%；
B: trifunctional epoxy resin's (non-flame resistant type epoxy resin):
B-1 epoxide equivalent is the tris phenol type epoxy of 162g/eq；
B-2 epoxide equivalent is the tris phenol type epoxy of 167g/eq；
B-3 epoxide equivalent is the tris phenol type epoxy of 172g/eq；
C: composite curing agent:
C-1 phenolic hydroxyl equivalent is the tung oil modified phenolic resin of 525g/eq；
C-2 phenolic hydroxyl equivalent is the tetrabromobisphenol A of 270g/eq；
C-3 phenolic hydroxyl equivalent is the phenol Linear phenolic resin of 105g/eq；
D: curing accelerator: 2-methylimidazole.
E: compounded mix:
E-1 diethyl hypo-aluminum orthophosphate, both melamine cyanurates are with 0.8:1.8 ratio compounding；
E-2 diethyl hypo-aluminum orthophosphate, both melamine cyanurates are with 1.0:2.0 ratio compounding；
E-3 diethyl hypo-aluminum orthophosphate, both melamine cyanurates are with 1.2:2.2 ratio compounding；
E-4 diethyl hypo-aluminum orthophosphate, both melamine cyanurates are with 0.5:2.5 ratio compounding；
E-5 diethyl hypo-aluminum orthophosphate, both melamine cyanurates are with 1.5:1.6 ratio compounding；
E-6 diethyl hypo-aluminum orthophosphate；
E-7 melamine cyanurate；
E-8 antimony oxide；
It is as follows using Examples 1 to 6 and the method for the resin combination production copper-clad laminate of comparative example 1~13:
By phosphorous epoxy resin, non-flame resistant type epoxy resin (tris phenol type epoxy), composite curing agent (tung oil-modified phenol Urea formaldehyde, tetrabromobisphenol A, phenol Linear phenolic resin), curing accelerator measure be added to the container according to the ratio, stirring keeps it mixed It closes uniformly, adds the compounded mix of proportional quantity, stirred evenly with high speed disperser, finally adjust solution solids content with solvent Glue is made to 72 ± 2%.
Resin combination composition glue liquid obtained above is impregnated using the dedicated wood pulp paper of CEM-1 or rag paper, through oven drying system Core material prepreg is obtained, by above-mentioned core material semi-solid preparation the piece number overlapping, fabric prepreg is equipped on the outside of lamination, then in fabric Copper foil is arranged in one or both sides on the outside of prepreg, is not particularly limited for the process conditions of heat pressure forming process, generally It is under 150~190 DEG C of program setting temperature, 4~8MPa of programmed pressure, program setting time 120min, through hot pressing At the copper-clad laminate of 1.6mm.
For above-mentioned manufactured copper-clad laminate, its anti-flammability, 288 DEG C of thermal stress, water absorption rate, T260 DEG C of heat point are tested Layer time, bending strength, test result are as shown in Table 3 and Table 4.
Each performance test methods are as follows:
A: it anti-flammability: is tested according to UL-94 standard.
B: it resistance to immersed solder: is immersed in the tin furnace that temperature is 288 DEG C, the corresponding time is recorded when substrate occurs and blisters or be layered
C: it water absorption rate: is measured according to IPC-TM-650 2.6.2.1 method.
The D:T260 thermally stratified layer time: refer to plate under 260 DEG C of set temperature, since the effect of heat layering occurs now As duration before this.If the time is greater than 60min, just terminate to test.
E: it bending strength: is measured according to IPC-TM-650 2.4.4B method.
The test result of 3 copper-clad laminate of table
The test result of 4 copper-clad laminate of table
Pass through table 3 and the available following of table 4:
Examples 1 to 8 all shows plate with preferable anti-flammability, resistance to dip solderability, heat resistance and lower water suction Rate.
Comparative example 1 and embodiment 1 are compared it is found that due to not using trifunctional epoxy resin's (triphenol type asphalt mixtures modified by epoxy resin Rouge), the resistance to dip solderability, heat resistance of comparative example 1 declines to a great extent, and water absorption rate also increases very much.
Comparative example 2 and embodiment 2 compare it is found that since using phosphorous epoxy resin, the anti-flammability of comparative example 2 does not become Difference, resistance to dip solderability, heat resistance also decrease.
Comparative example 3 and embodiment 3 compare it is found that since the dosage of phosphorous epoxy resin and non-flame resistant type epoxy resin does not exist Within the scope of claim limits, the anti-flammability of comparative example 3 is deteriorated, and resistance to dip solderability, heat resistance declines to a great extent.
Comparative example 4 and embodiment 1 compare it is found that since using tung oil modified phenolic resin, the bending of comparative example 4 is not strong Degree significantly increases, degraded toughness.
Comparative example 5 and embodiment 2 compare it is found that since using tetrabromobisphenol A, the anti-flammability of comparative example 5 does not obviously become Difference.
Comparative example 7 and embodiment 7 compare it is found that due to having only used normal linear phenolic resin curing agent, comparative example 7 Anti-flammability is obviously deteriorated, and bending strength also significantly increases, and will affect plate machining property.
Comparative example 8 and embodiment 6 compare it is found that since the dosage of each component in composite curing agent does not limit in claim Within the scope of fixed, the anti-flammability of comparative example 8, resistance to dip solderability, heat resistance are obviously deteriorated, and water absorption rate also significantly increases.
Comparative example 9 and embodiment 5 compare it is found that since the dosage of each component in compounded mix does not limit in claim Within the scope of, the anti-flammability of comparative example 9, resistance to dip solderability, heat resistance are obviously deteriorated, and water absorption rate also significantly increases.
Comparative example 10 and embodiment 2 compare it is found that since the dosage of each component in compounded mix does not limit in claim Within the scope of fixed, the anti-flammability of comparative example 10, resistance to dip solderability, heat resistance are obviously deteriorated, and water absorption rate also significantly increases.
Comparative example 11 and embodiment 8 compare it is found that due to only single use diethyl hypo-aluminum orthophosphate, comparative example 11 it is fire-retardant Property be deteriorated, resistance to dip solderability, heat resistance also declines to a great extent, and water absorption rate also increases very much.
Comparative example 12 and embodiment 1 compare the resistance of comparative example 12 it is found that due to only single use melamine cyanurate Combustion property is deteriorated, and resistance to dip solderability, heat resistance also declines to a great extent, and water absorption rate also increases very much.
As known from compared to Example 7, the water absorption rate of embodiment 7, resistance to dip solderability, heat resistance are superior to comparative example to comparative example 13 13.Illustrate that phosphorous epoxy resin, polyfunctional epoxy resin and the collocation of phosphorus nitrogen compounded mix use, not only can be improved fire-retardant Property, moreover it is possible to the crosslink density of solidfied material is effectively improved, heat resistance, the resistance to dip solderability and water imbibition of plate are improved.
In conclusion the bromo- phosphorus-nitrogen coordinated fire-retardant technology of phosphorus-of the present invention, having broken tradition has halogen CEM-1 to cover copper foil In laminate halogen antimony cooperative flame retardant system can not substituted technical bottleneck, completely removed the antimony containing compounds in CEM-1, reached Limitation requirement of the international environment regulation to antimony containing compounds is arrived.
There is halogen without the preparation-obtained CEM-1 copper-clad laminate of antimony resin combination, anti-flammability using of the invention The peer for having reached halogen antimony synergistic system is horizontal, the V-0 grade standard in UL-94, meanwhile, 288 DEG C of thermal stress are increased to 140~ 148s improves 36~39% compared with halogen antimony collaboration system, and water absorption rate is reduced to 0.07~0.09%, with halogen antimony collaboration system Compared to reducing 25~41%；T260 is increased to 50~56min, improves 36~42% compared with halogen antimony collaboration system.Thus, This has halogen without antimony CEM-1 copper-clad laminate while guaranteeing fire-retardant, and it is outstanding comprehensive also to have high heat resistance, high wet-heat resisting etc. It can advantage.
The Applicant declares that the present invention is explained by the above embodiments of the invention have halogen without antimony resin combination, uses Its prepreg, laminate and printed circuit board, but the present invention is not limited to the above embodiments, that is, does not mean that the present invention must Above-described embodiment, which must be relied on, to be implemented.It should be clear to those skilled in the art, any improvement in the present invention, right The equivalence replacement of each raw material of product of the present invention and addition, the selection of concrete mode of auxiliary element etc., all fall within guarantor of the invention It protects within range and the open scope.

Claims (10)

1. one kind has halogen without antimony resin combination, which is characterized in that described to have halogen without antimony resin combination include following parts by weight Component:
20 parts~50 parts phosphorous epoxy resins, 20 parts~50 parts non-flame resistant type epoxy resin, 20 parts~60 parts composite curing agents, 0.05 part~1.0 parts curing accelerators and 10 parts~50 parts compounded mixs；The compounded mix is phosphorous flame-retardant material and nitrogen system The combination of fire proofing, the composite curing agent are the composite curing agent containing halogen.
2. according to claim 1 have halogen without antimony resin combination, which is characterized in that phosphorus contains in the phosphorous epoxy resin Amount is 2%~4%；
Preferably, the phosphorous epoxy resin is DOPO base epoxy, ODOPB base epoxy, three phosphonitrile base asphalt mixtures modified by epoxy resin of ring In rouge or diphenyl phosphine oxide epoxy resin any one or at least two combination；
Preferably, the degree of functionality of the non-flame resistant type epoxy resin is 2~4；
Preferably, the non-flame resistant type epoxy resin is bisphenol A type epoxy resin (such as bisphenol A-type novolac epoxy resin), double Phenol F type epoxy resin, biphenyl type epoxy resin, alkyl phenol epoxy resin, DCPD-containing epoxy resin o-cresol type phenolic aldehyde ring Oxygen resin, phenol type novolac epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin any one or at least two Combination；
Preferably, the epoxide equivalent of the non-flame resistant type epoxy resin be 100g/eq~800g/eq, preferably 100g/eq~ 300g/eq。
3. according to claim 1 or 2 have halogen without antimony resin combination, which is characterized in that the composite curing agent is with it Total weight is 100% meter, including following weight percentage components: 25%~55% plant oil modified phenol-formaldehyde resin, 15% ~50% bromination phenolic compound and 10%~40% linear phenolic resin；
Preferably, the equivalent of the reactive group to react in the composite curing agent with epoxy group is 100~700g/eq；
Preferably, the phenolic hydroxyl equivalent of the plant oil modified phenol-formaldehyde resin is 400~550g/eq, the bromination phenols chemical combination The phenolic hydroxyl equivalent of object is 200~300g/eq, and the phenolic hydroxyl equivalent of the linear phenolic resin is 100~250g/eq；
Preferably, the plant oil modified phenol-formaldehyde resin is tung oil modified phenolic resin, epoxy soybean oil modified phenolic resin, waist Any one in fruit phenol phenol-formaldehyde resin modified, modification of flax oil phenolic resin or castor oil modified phenolic resin or at least two Combination；
Preferably, the bromine content of the bromination phenolic compound is 19%~58%；
Preferably, the bromination phenolic compound be tetrabromobisphenol A, tribromphenol or bromination phenolic aldehyde in any one or extremely Few two kinds of combination；
Preferably, the linear phenolic resin be phenol type phenolic resin, bisphenol A type phenolic resin, o-cresol type phenolic resin, In triphenol phenolic resin, naphthalene type phenolic resin, biphenyl type phenolic resin or dicyclopentadiene phenolic resin any one or extremely Few two kinds of combination.
4. according to any one of claim 1-3 have halogen without antimony resin combination, which is characterized in that the compounded mix The weight ratio of middle phosphorous flame-retardant material and nitrogen series anti-flaming material is (0.8~1.2): (1.8~2.2)；
Preferably, the phosphorous flame-retardant material is dimethyl hypo-aluminum orthophosphate, second diyl zinc hypophosphite, ammonium polyphosphate, diethyl Aluminum phosphate, aminomethyl phenyl hypo-aluminum orthophosphate, aminomethyl phenyl zinc hypophosphite, hydroxymethyl phenyl hypo-aluminum orthophosphate, gathers dimethyl zinc hypophosphite Phosphenylic acid diphenyl sulphone (DPS) ester, diethyl zinc hypophosphite, second diyl hypo-aluminum orthophosphate, any one in hydroxymethyl phenyl zinc hypophosphite Or at least two combination；Further preferred diethyl hypo-aluminum orthophosphate；
Preferably, the nitrogen series anti-flaming material is cyanurate, melamine phosphate, melamine borate salt, melamine Amine cyanurate, melamine pyrophosphate, melamine polyphosphate, in phosphonitrile any one or at least two group It closes, further preferred melamine cyanurate；
Preferably, the average grain diameter of the compounded mix is 1~5 μm.
5. having halogen without antimony resin combination described in any one of -4 according to claim 1, which is characterized in that the solidification promotes Agent is any one or at least two in tertiary amine, three-level phosphine, metal-organic complex, quaternary ammonium salt or glyoxaline compound Combination；
Preferably, the glyoxaline compound is 2-methylimidazole, -4 methylimidazole of 2- ethyl, 2- phenylimidazole, 2- phenyl -4 In methylimidazole or 1- 1-cyanoethyl-2-methylimidazole any one or at least two mixture.
6. a kind of resin adhesive liquid, the resin adhesive liquid is that have halogen without antimony resin group for according to any one of claims 1 to 5 Conjunction object, which is dissolved or dispersed in solvent, to be obtained；
Preferably, the solvent is methanol, ethyl alcohol, acetone, butanone, ethylene glycol monobutyl ether, methyl acetate, ethyl acetate or hexamethylene In ketone any one or at least two mixing；
Preferably, the solid content of the resin adhesive liquid is 60%~80%, particularly preferred 65%~75%.
7. a kind of prepreg, which is characterized in that the prepreg includes reinforcing material and adheres to thereon after being dried by impregnation It is according to any one of claims 1 to 5 to have halogen without antimony resin combination；
Preferably, the reinforcing material is wood pulp paper or rag paper.
8. a kind of laminate, which is characterized in that the laminate includes an at least prepreg as claimed in claim 7.
9. a kind of metal-clad laminate, which is characterized in that the metal-clad laminate contains at least one such as claim 7 The metal foil of the prepreg and the prepreg one or both sides being overlying on after overlapping.
10. a kind of printed circuit board, which is characterized in that the printed circuit board include laminate as claimed in claim 8 or Metal-clad laminate as claimed in claim 9.
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