CN110066493A - A kind of halogen-free resin composition, prepreg and the laminate of low dielectric low dielectric loss - Google Patents

A kind of halogen-free resin composition, prepreg and the laminate of low dielectric low dielectric loss Download PDF

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Publication number
CN110066493A
CN110066493A CN201910300128.2A CN201910300128A CN110066493A CN 110066493 A CN110066493 A CN 110066493A CN 201910300128 A CN201910300128 A CN 201910300128A CN 110066493 A CN110066493 A CN 110066493A
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resin
low dielectric
halogen
epoxy resin
weight
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田堃
盛佳炯
彭康
沈宗华
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Hangzhou Hua Zheng Xin Materials Co Ltd
New Materials Co Ltd Zhejiang China Is
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Hangzhou Hua Zheng Xin Materials Co Ltd
New Materials Co Ltd Zhejiang China Is
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    • 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
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
    • 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
    • C08G59/50—Amines
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08J2461/04, C08J2461/18, and C08J2461/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/04—Polysiloxanes
    • C08J2483/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention discloses Halogen resin combination, prepreg and the laminates of a kind of low dielectric low dielectric loss.Wherein halogen-free resin composition includes following material: 100 parts by weight of epoxy resin；2~45 parts by weight of double-deck type silsesquioxane curing agent；Cyanate modified 10~50 parts by weight of polyphenylene oxide resin；10~25 parts by weight of phenylpropyl alcohol oxazines resin；0.001~5 parts by weight of promotor.The present invention is with a kind of silsesquioxane curing agent of special construction, pass through graft copolymerization, obtain the resin material of outstanding dielectric properties, high Tg, since there is higher stability of molecule and lower sub-chain motion ability after its solidification, thus with the metal-coated laminated board dielectric properties of this resin preparation, heat resistance, mechanical property and resistance to hygroscopicity etc. are enhanced.

Description

A kind of halogen-free resin composition, prepreg and the laminate of low dielectric low dielectric loss
Technical field
The present invention relates to prepreg, the laminates of a kind of halogen-free resin composition, and its preparation, belong to printed circuit board Basic manufacturing field.
Background technique
With the fast development of science and technology and deepening constantly for people's environmental consciousness and theory, halogen-free product becomes instantly One of the urgent need of world's every profession and trade, especially electronic product industry.World community and related industry alliance also release successively Corresponding policies and regulations are made that accurate limitation to halogen in product, especially chlorine class, bromine class content, to leaded, mercury, cadmium It is managed Deng the product to life harmful element, under this situation, develops novel high-performance, there is environmental-friendly profile Material has become one of the direction of most critical in current industry.
The very fast development of information technology in recent years, the letter of the electronic circuits product such as mobile communication, server, mainframe computer Breath processing, and the information storage technology constantly updated constantly realize covering, and the signal processing and transmission speed of various kinds of equipment are not Disconnected to be promoted, the equipment baseplate material of higher performance has become one of production firm's research and development instantly and the heat subject of manufacture.In order to It maintaining transmission rate and keeps transmission signal integrity, baseplate material not only needs lower dielectric constant and dielectric loss, And in order to still electronic building brick be maintained to operate normally under hot and humid environment, baseplate material also needs to have excellent heat-resisting Property, higher glass transition dimension, high humidity resistance and compared with low water absorbable grade high reliability feature.In traditional Halogen substrate The common curing agent of epoxy resin has polyamines, acid anhydrides, phenolic resin etc..As in amine, this kind of molecular structure of phenolic resin due to Its structure feature itself, so that the water absorption rate of solidfied material rises, wet-hot aging performance and dielectric properties decline.And acid anhydride type curing agent Reactivity it is poor, it is desirable that condition of cure harshness.
The above problem that occurs when to solve Common Curing Agents cured epoxy resin, polyhedral oligomeric silsesquioxane (with Lower abbreviation POSS) this novel hybrid inorganic-organic structure nano material, in recent years by extensive concern in the world.It compares Traditional polymer modification material, POSS, which is gathered around, to be had the following advantages: first from structure, POSS molecular dimension only has 1~3 nanometer, Main body is the solid space structure of cage modle or half cage modle, and molecular density is lower, and the symmetry of height makes it possess excellent Jie Electrical property (Dk=2.43)；Secondly, its main body framework is made of Si-O-Si key, such approximation inorganic structure possesses POSS Excellent heat resistance and anti-flammability, product is mainly silica composition after thermal degradation, has widened it in the application of flame retardant area； Finally, each apex angle functional group of POSS skeleton periphery is modified by a variety of modified methods such as grafting, activation, to meet difference Practical use.
United States Patent (USP) US20140367149 uses the full cage modle POSS of octa-epoxy as resin curing agent, prepares layer Pressing plate and multi-layer board etc..This cagelike structure reactivity for possessing eight epoxy groups is very strong, but eight functional group's space bits Hinder larger, reaction efficiency is general.However, full cagelike structure itself has stronger inertia, while improving its system heat resistance, Also because its dissolubility and compatibility are poor, phenomena such as easily reunion, so that the impact resistant strength of system is general, it is overall tough Property is poor.
Chinese patent CN 102815071B, is used the silsesquioxane of monoisocyanates base, is introduced using grafting method Epoxy molecule chain, so as to avoid tradition blending or the easily caused agglomeration of eight structure of functional groups, from molecule angle pair Epoxy chain is enhanced, and is significantly improved to the mechanics and heat resistance of material.But due to the rigid structure and list of POSS itself The asymmetry of modified with functional group, so that the dielectric properties of whole system are declined.
Summary of the invention
In view of prior art defect, the purpose of the present invention is to provide a kind of Halogen resin combinations of low dielectric low dielectric loss Object, prepreg and laminate.Halogen-free resin composition of the invention is that one kind has lower dielectric constant and dielectric loss, High glass-transition temperature, low water absorbable, high-fire resistance, anti-flammability and the ep-type material easily stored.Semi-solid preparation of the invention Piece and laminate have excellent heat resistance, high glass-transition temperature, low water absorption, excellent anti-flammability, low-k And low dielectric loss and good resistance to ag(e)ing.
In order to achieve the object of the present invention, the present invention takes following technical scheme:
A kind of Halogen resin combination of low dielectric low dielectric loss includes following material: 100 parts by weight of epoxy resin；Double first 2~45 parts by weight of template silsesquioxane curing agent；10~50 parts by weight of polyphenylene oxide resin；10~25 weight of benzoxazine resin Part；0.001~5 parts by weight of promotor.
The present invention using the double-deck type silsesquioxane with reactive ester group as curing agent, not only may be used by this curing agent Dielectric constant, dielectric loss and the water-fast effect of resin material are reduced, and is enhanced from molecule angle, material is further increased The glass transition temperature of material, heat resistance, anti-flammability and mechanical property etc. have practical application value in electronics field.
Preferably, the epoxy resin be halogen-free type low dielectric-epoxy resin, can be selected from bisphenol A type epoxy resin, Bisphenol f type epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, phenol aldehyde modified epoxy resin, naphthalene nucleus type epoxy resin, virtue Alkyl linear phenolic epoxy resin, phenyl alkanes based epoxy resin, isocyanate modified epoxy resin, alicyclic ring same clan asphalt mixtures modified by epoxy resin One or more of rouge, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, modified epoxy containing unsaturated bond Composition.
Preferably, the double-deck type silsesquioxane curing agent, the oligomeric high activity to have following structure is consolidated Agent,
Wherein, R1For one or more of alkenyl, amino, long-chain fat base, alcyl and aromatic radical, R2For hydroxyl, contain The one or more of the alkyl of unsaturated group, amino, ether, ester group；It is 2~45 parts as preferred number, more preferably It is 10~40 parts, unobvious for the optimization of dielectric and hot property if usage amount is less than 2 parts, if usage amount is greater than 45 parts, have Phenomena such as being likely to occur poor compatibility, part reunion or layering.
Preferably, the molecular weight of the polyphenylene oxide resin in 1000 to 5000 ranges, can be containing alkyl, hydroxyl Base, alkenyl, alkynyl or aryl polyphenylene oxide resin one or more of resin combinations.
Preferably, the benzoxazine resin, is selected from bisphenol A-type benzoxazine resin, bisphenol-f type benzoxazine tree Rouge, the one or more combination object of allyl bisphenol A-type benzoxazine resin.
Preferably, promotor can be known any promotor for accelerating curing rate；For example, the promotor It can be or mixtures thereof imidazoles, organic metal salt, imidazoles is selected from 2-methylimidazole, 2- phenylimidazole or 2- ethyl -4- methyl Imidazoles；Organic metal salt is selected from zinc octoate, zinc Isoocatanoate, stannous octoate, dibutyl tin dilaurate, zinc naphthenate, aphthenic acids Cobalt, aluminium acetylacetonate, acetylacetone cobalt or acetylacetone copper.
Preferably, proper auxiliary materials, auxiliary agent, including filler can also be added, and solvent, fire retardant, toughener, coupling agent, Dispersing agent etc., the compound that composition properties are improved.
Preferably, the filler is selected from crystalline sillica, fused silica, nucleocapsid silica, poly- silicon oxygen Alkane powder, silicone rubber powder, polysiloxanes spherical rubber powder, aluminium oxide, aluminium hydroxide, the boron nitride, two for coating silicone resin Titanium oxide, barium sulfate, barium titanate, one or several kinds of compositions in talcum powder.
Preferably, the fire retardant is halogen-free flame retardants, it is selected from phosphorus flame retardant, nitrogenated flame retardant, silicon-series five-retardant, And the one or more combination object of the synergistic fire retardants such as other phosphorus nitrogen silicon.
Preferably, the phosphorus content of the halogen-free resin composition is controlled 1~5%.
A kind of prepreg, including nonwoven glass-fiber-fabric reinforcing material and by impregnation it is dry after be attached on reinforcing material as before The halogen-free resin composition.
Above-mentioned prepreg carries out as follows: above-mentioned halogen-free resin composition being mixed evenly, dispersion is made Uniform prepreg；Prepreg above-mentioned is impregnated by glass-fiber-fabric, then toasts 2~15 minutes, can be prepared by 80~180 DEG C The prepreg.
A kind of laminate, the laminate is by including one or two layers metal foil and one layer or more foregoing semi-solid preparation Piece.
Above-mentioned laminate carries out as follows: and by above-mentioned prepreg, one or more layers is superimposed with each other that form half solid Change lamella, metal foil is covered in the one or both sides of layer of prepreg, in 0.5MPa~5MPa pressure and 150 DEG C~250 DEG C temperature Degree lower compacting forms for 1-5 hours.
The present invention has the following technical effect that
(1) halogen-free resin composition of the invention, have excellent heat resistance, high glass-transition temperature, low water absorption, The advantages that excellent anti-flammability, low-k and low dielectric loss factor.
(2) prepreg and laminate produced by the present invention have excellent heat resistance, high glass-transition temperature, low suction Water rate, excellent anti-flammability, low-k and low dielectric loss and good resistance to ag(e)ing.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be to the embodiment of the present invention Technical solution carries out clear, complete description.Obviously, described embodiment is a part of the embodiments of the present invention, rather than Whole embodiments.Based on described the embodiment of the present invention, those of ordinary skill in the art are without creative work Under the premise of every other embodiment obtained, belong to protection scope of the present invention.
Unless otherwise defined, technical term or scientific term used in the disclosure are should be in fields of the present invention The ordinary meaning for thering is the personage of general technical ability to be understood.
Part raw material used in embodiment:
Epoxy resin 1: DCPD-containing epoxy resin；
Epoxy resin 2:Dopo-HQ type phosphorous epoxy resin；
Epoxy resin 3: isocyanate modified epoxy resin；
Epoxy resin 4: biphenyl type epoxy resin；
Benzoxazine resin (BZ): bisphenol-f type benzoxazine resin；
Polyphenylene oxide (PPO): modified terminal hydroxy group polyphenylene oxide；
Phosphonium flame retardant: phosphorus cyanogen based flame retardant；
Inorganic filler: fused silica, silane coupling agent processing, 525ARI；
Promotor: diethyl tetramethyl imidazoles, 2E4MZ.
Embodiment 1
Extracting epoxy resin 1:30 parts by weight, epoxy resin 2:30 parts by weight, epoxy resin 3:20 parts by weight, epoxy resin 4: 20 parts by weight, double-deck POSS:40 parts by weight, benzoxazine resin (BZ): 20 parts by weight, polyphenylene oxide (PPO): 30 parts by weight, Dimethylamino naphthyridine (DMAP): 0.15 parts by weight, phosphonium flame retardant: 15 parts by weight, acetylacetone cobalt: 0.04 parts by weight, with having Solvent dissolution, the solid content for adjusting resin combination are 65wt%, at room temperature in the appearance equipped with blender and condenser Device internal modulation is at prepreg.
The halogen-free resin composition is impregnated and is coated on E type glass cloth (2116,105 ± 3g/m of substance2) on, and The prepreg of resin content 50% is made after toasting in 170 DEG C of baking ovens.
By the prepreg of resin content 50% obtained, a copper foil is respectively put up and down, is placed in vacuum hotpressing machine and suppresses Obtain copper-clad laminate.Specific process for pressing is to press 2 hours at a temperature of 200 DEG C under 2MPa pressure.
According to IPC-TM650 detection method, dielectric constant (Dk), the dielectric loss factor of copper-clad laminate are detected (Df), performances, the concrete outcome such as glass transition temperature (Tg), peel strength, heat resistance, water absorption rate, anti-flammability are shown in Table 2.
The resin combination of embodiment 2~6 and comparative example 1~6, prepreg, copper-clad laminate preparation method with Embodiment 1 is identical, and concrete component ratio is shown in that Tables 1 and 2, test result are shown in Table 3 and table 4.
Table 1
Table 2
Table 3
Table 4
It is copper foil covered as comparison above data it is found that copper clad laminate performance made from according to the present invention is excellent Pressing plate has lower dielectric constant and dielectric loss, possesses excellent heat resistance, lower water absorption rate, higher vitrifying turn Temperature, flame retardant property reach V0 grades, even can be seen that more single matrix resin from embodiment 4-6, in hot property It is significantly improved with still having in terms of dielectricity, and comparative example 4-6 shows each component played in entire resin combination Synergistic effect, therefore, this novel POSS is a kind of efficient crosslinking agent of excellent combination property, and described in the invention is this Resin combination is able to satisfy the application requirement of high-speed high frequency circuit substrate.
The method of the present invention that the above embodiments are only used to help understand and its core concept.It should be pointed out that for For those skilled in the art, without departing from the principle of the present invention, if can also be carried out to the present invention Dry improvement and modification, these improvement and modification are also fallen into the claims in the present invention protection scope.

Claims (10)

1. a kind of Halogen resin combination of low dielectric low dielectric loss, which is characterized in that include following material: 100 weight of epoxy resin Measure part；2~45 parts by weight of double-deck type silsesquioxane curing agent；10~50 parts by weight of polyphenylene oxide resin；Benzoxazine resin 10~25 parts by weight；0.001~5 parts by weight of promotor.
2. a kind of Halogen resin combination of low dielectric low dielectric loss according to claim 1, which is characterized in that the ring Oxygen resin is halogen-free type low dielectric-epoxy resin, can be selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, phosphorous asphalt mixtures modified by epoxy resin Rouge, nitrogen-containing epoxy thermoset, phenol aldehyde modified epoxy resin, naphthalene nucleus type epoxy resin, aralkyl linear phenolic epoxy resin, octadecyloxy phenyl Hydro carbons epoxy resin, isocyanate modified epoxy resin, alicyclic based epoxy resin, dicyclopentadiene type epoxy resin, biphenyl One or more of type epoxy resin, modified epoxy containing unsaturated bond composition.
3. a kind of Halogen resin combination of low dielectric low dielectric loss according to claim 1, which is characterized in that described is double Deck type silsesquioxane curing agent, for the oligomeric high activity curing agent having following structure,
Wherein, R1For one or more of alkenyl, amino, long-chain fat base, alcyl and aromatic radical, R2For hydroxyl, contain insatiable hunger With the one or more of the alkyl of group, amino, ether, ester group.
4. a kind of Halogen resin combination of low dielectric low dielectric loss according to claim 1, which is characterized in that described is poly- Phenylene ether resins molecular weight is in 1000 to 5000 ranges, selected from the polyphenylene oxide resin containing alkyl, alkenyl, hydroxyl, alkynyl or aryl One or more of resin combinations.
5. a kind of Halogen resin combination of low dielectric low dielectric loss according to claim 1, which is characterized in that the benzene And oxazines resin is selected from bisphenol A-type benzoxazine resin, bisphenol-f type benzoxazine resin, allyl bisphenol A-type benzoxazine tree The one or more combination object of rouge.
6. a kind of Halogen resin combination of low dielectric low dielectric loss according to claim 1, which is characterized in that the promotion Agent is or mixtures thereof imidazoles, organic metal salt.
7. a kind of Halogen resin combination of low dielectric low dielectric loss according to claim 1, which is characterized in that the Halogen Resin combination further includes filler, and filler is selected from crystalline sillica, fused silica, nucleocapsid silica, poly- silicon oxygen Alkane powder, silicone rubber powder, polysiloxanes spherical rubber powder, aluminium oxide, aluminium hydroxide, the boron nitride, two for coating silicone resin Titanium oxide, barium sulfate, barium titanate, one or several kinds of compositions in talcum powder.
8. a kind of Halogen resin combination of low dielectric low dielectric loss according to claim 1, which is characterized in that further include nothing Halogen fire retardant, one selected from synergistic fire retardants such as phosphorus flame retardant, nitrogenated flame retardant, silicon-series five-retardant and other phosphorus nitrogen silicon Kind or several compositions.
9. a kind of prepreg, including nonwoven glass-fiber-fabric reinforcing material and by impregnation it is dry after be attached on reinforcing material such as right It is required that Halogen resin combination described in 1-8.
10. a kind of laminate, the laminate includes one or two layers metal foil and one layer or more as claimed in claim 9 half Cured sheets.
CN201910300128.2A 2019-04-15 2019-04-15 A kind of halogen-free resin composition, prepreg and the laminate of low dielectric low dielectric loss Pending CN110066493A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111732817A (en) * 2020-06-19 2020-10-02 林州致远电子科技有限公司 Halogen-free low-loss copper-clad plate and glue solution and preparation method thereof
CN114292404A (en) * 2021-12-30 2022-04-08 广东盈骅新材料科技有限公司 POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105348743A (en) * 2015-12-07 2016-02-24 浙江华正新材料股份有限公司 Halogen-free resin composition, prepreg and laminated board
CN107118351A (en) * 2017-05-17 2017-09-01 浙江大学 Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105348743A (en) * 2015-12-07 2016-02-24 浙江华正新材料股份有限公司 Halogen-free resin composition, prepreg and laminated board
CN107118351A (en) * 2017-05-17 2017-09-01 浙江大学 Double-deck silsesquioxane epoxy resin modification agent and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SAYANTAN ROY ET AL.: "《Exploiting POSS-Sorbitol Interactions: Issues of Reinforcement of Isotactic Polypropylene Spun Fibers》", 《MACROMOLECULES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111732817A (en) * 2020-06-19 2020-10-02 林州致远电子科技有限公司 Halogen-free low-loss copper-clad plate and glue solution and preparation method thereof
CN114292404A (en) * 2021-12-30 2022-04-08 广东盈骅新材料科技有限公司 POSS (polyhedral oligomeric silsesquioxane) modified oxazoline derivative, preparation method thereof and epoxy resin composition

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Application publication date: 20190730