CN103467982B - Cyanate compositions and prepare the method for copper-clad plate with it - Google Patents
Cyanate compositions and prepare the method for copper-clad plate with it Download PDFInfo
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Abstract
The present invention discloses a kind of cyanate compositions, said composition specifically comprises cyanic acid ester, low-molecular polyphenylene ether, olefinic monomer, organometallic salt catalysts and mineral filler, environmental protection fire retarding agent and organic solvent, the invention also discloses and a kind of adopt this cyanate compositions and prepare the method for copper-clad plate. The low-molecular polyphenylene ether that the present invention processes through redistribution reaction obtain by introducing, solve the shortcoming of macromolecule polyphenylene oxide mobility difference, add the consistency that monomer alkene improves system further simultaneously, and on the dielectric properties of system without obvious impact, said composition can be used for manufacturing high performance copper-clad plate green, environmental protection, and the copper-clad plate of the type has the performance of outstanding dielectric properties, thermotolerance and environmental protection flame retardant.
Description
Technical field
The present invention relates to field of compound material, it is specifically related to a kind of method taking cyanate ester resin as the composition of matrix resin and preparing copper-clad plate.
Background technology
Along with the height of semiconducter device is integrated and the becoming more meticulous of packaging process, the densification of printing line circuit, connect the progress with field engineering, electron device develops to the direction of miniaturization, high frequency, high speed digitizing, high reliability significantly, is particularly applied in the field of mobile communication of high frequency. As the printed circuit board of electronic device substrate, the trend development of recent oriented multiple stratification, super-refinement circuit, thus the transmission speed of signal must be more and more faster, the frequency of signal is also more and more higher, therefore this also requires that the printed wiring panel material as Signal transmissions carrier must reduce its specific inductivity, simultaneously the dielectric loss factor of material is also enough low, thus makes the loss of signal in transmitting procedure less. Originally conventional FR-4 copper-clad plate uses epoxy resin as matrix resin always, but the dielectric properties of epoxy resin can not meet requirement, therefore needs the material using displaced loop oxygen system.
On the other hand, the halogen contained compound with good flame retardant effect as the main fire retardant material of printed circuit board is bigger to environmental influence because of it always before, and various countries are more and more higher to environmental requirement, existing many halogen flame retardant fire retardants are prohibited from using, therefore use this kind of environmentally harmful halogen flame for avoiding, develop and the environmental protection fire retarding agent that uses halogen and have a good flame retardant effect has become the task of top priority.
Cyanic acid ester (cyanateester, it is called for short CE) it is containing the derivative of two and the phenol of two or more cyanate group, occurring three poly-cyclizations to generate high crosslink density, nonpolarity aryloxy triazine ring structures under the effect of heat and catalyzer, this kind of structure makes cyanic acid ester have excellent dielectric properties just. The cyanic acid ester of solidification also has fire-retardant, high glass-transition temperature, low-shrinkage, low rate of moisture absorption, good adhesive property and low be fuming and the performance such as resistance to ablation preferably simultaneously, it it is the body material of performance resins based composites, having a wide range of applications in many fields such as electronics, aerospace, military projects, particularly there is bigger development prospect the aspect such as high frequency printed circuit boards, structured material and antenna coating.
Although cyanate ester resin is compared with the thermosetting resins such as epoxy resin, bismaleimides (BMI), its impact resistance is better, but its toughness still can not meet requirement, it need to be carried out modification, usually adopt the thermoplastic resin with higher thermal characteristics that it is carried out modification. As United States Patent (USP) 4157360,4983683 and 4902752 etc. respectively describes the thermoplastic polymers such as polyterephthalate carbonic ether, polysulfones to the modification of cyanate ester resin, but the matrix material that these patents are mentioned is not containing fire retardant, it is be not suitable in the electronic application field that flame-retardancy requirements is higher such as printed electronic circuit board industry.
United States Patent (USP) 7208539,4496695 and Japanese Patent 05339342 describe cyanic acid ester and the blend of epoxy resin or brominated epoxy resin, United States Patent (USP) 4097455 and United States Patent (USP) 4782178 describe the matrix material of cyanogen bromide acid esters, although such matrix material has flame retardant effect, but it is known that, compared with cyanate ester resin, the dielectric properties of epoxy resin are poor, thus the dielectric properties causing matrix material deteriorate, and its thermal characteristics also can not compare favourably with cyanate ester resin.
United States Patent (USP) 6162876, it may also be useful to the conventional flame retardant that the addition such as antimonous oxide, antimony peroxide is bigger, the performance of matrix material has bigger impact by this; United States Patent (USP) 7816430 employs the organic fire-retardant containing bromine such as brominated Polystyrene, hexabromocyclododecane, and due to fire-retardant requirement, generally the addition of this kind of interpolation sex flame retardant is all excessive, causes the thermotolerance of sheet material and wet-hot aging performance poor.
Polyphenylene oxide (polyphenyleneoxide/polyphenyleneether, it being called for short PPO/PPE) resin has higher mechanical strength and thermotolerance, good stability of the dimension, rate of moisture absorption is low, dielectric properties are outstanding, specific inductivity and dielectric loss factor are not almost subject to the impact of temperature and frequency very little, it is possible to when cyanate ester resin is carried out modification by its other thermoplastic polymer of the epoxy resin before improvement, deteriorate the problem of the partial properties of cyanic acid ester.
As the thermoplastic resin of a kind of high molecular, the fusing point of polyphenylene oxide resin is higher, if the glue liquid that use polyphenylene oxide and cyanic acid ester simply mix is to make the prepreg of copper-clad plate, when carrying out hot pressing and manufacture printed circuit board, owing to the polyphenylene oxide viscosity of high molecular is higher, cause prepreg mobility too low so that the cohesiveness between insulating material and Copper Foil is poor, polymkeric substance can not fill the blank between prepreg and Copper Foil effectively, thus easily causes cavity and white point. Therefore it is first necessary to polyphenylene ether resin carries out modification, redistribution reaction can reduce molecular weight and the flowing property of polyphenylene oxide, can introduce reactive group again, it is to increase the reactive behavior of matrix on its molecular backbone chain.
Summary of the invention
Technical problem to be solved by this invention is to provide the good copper-clad plate cyanate resin composition of a kind of environmental protection flame retardant, dielectric properties, said composition comprises 100 parts of cyanic acid esters, 25��65 parts of low-molecular polyphenylene ethers, 5��135 parts of olefinic monomers, 0.05��0.2 part of organometallic salt catalysts by weight, and mineral filler, environmental protection fire retarding agent and organic solvent.
Further, above-mentioned cyanate ester resin can be a kind of in bisphenol A cyanate ester, bisphenol E-type cyanate, bisphenol-f type cyanic acid ester, bis-phenol M type cyanic acid ester, tetramethyl-bisphenol-f type cyanic acid ester, dicyclopentadiene bisphenol A cyanate ester or wherein multiple combination.
Its chemical structural formula is:
R1For the one in following structure
R2��R3For hydrogen atom or methyl group, these four groups may be the same or different. Such as, bisphenol A cyanate ester, bisphenol E-type cyanate, bisphenol-f type cyanic acid ester, bis-phenol M type cyanic acid ester, tetramethyl-bisphenol-f type cyanic acid ester, dicyclopentadiene type ethylene rhodanate etc. This cyanic acid ester preferably containing 50��70% tripolymers (namely by cyanate ester monomer from poly-and formed containing triazine ring structure) performed polymer.
Further, above-mentioned cyanic acid ester organic metal salt curing catalysts can be the isocaprylic acid metal-salts such as isocaprylic acid zinc, cobalt iso-octoate, isocaprylic acid chromium; The acetyl acetone salts such as acetylacetone cobalt, zinc acetylacetonate, acetylacetone copper, ferric acetyl acetonade and manganese acetylacetonate; A kind of or wherein multiple combination in the metallic naphthenates such as cobalt naphthenate, zinc naphthenate, naphthenic acid titanium and manganese naphthenate.
Further, above-mentioned mineral filler can aluminium hydroxide, magnesium hydroxide, silicon-dioxide, hollow glass micro-ball, mica, clay, talcum powder, kaolin, aluminum oxide, titanium oxide, beryllium oxide, silicon nitride, boron nitride, barium sulfate, barium titanate, strontium titanate, calcium titanate, pure aluminium silicate, Calucium Silicate powder, Magnesium Silicate q-agent, aluminum borate.
Further, it is preferable that the particle diameter of above-mentioned filler is 0.05��2 micron.
Further, above-mentioned fire retardant can adopt triphenylphosphate, Tritolyl Phosphate, trioctyl phosphate, diphenyl octyl phosphate, phosphate diphenyl isodecyl ester, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid hexichol trimethylphenylmethane ester, phosphoric acid hexichol isopropyl phenyl ester, Resorcinol two [two (2, 6-3,5-dimethylphenyl) phosphoric acid ester], the phosphoric acid ester fire retardants such as diphenyl 2 ethylhexyl phosphate, or methylethyl phospho acid aluminium, aluminum diethylphosphinate, the phosphinate flame retardant such as hydroxymethyl phenyl phospho acid aluminium, or 3-hydroxy phenyl phosphorus acyl propionic acid, hydroxyl phenylphosphorous acid propionic acid, hydroxy-propionic acid base phenylphosphorous acid, 2-carboxy ethyl (phenyl) phospho acid etc. or 9, 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO), combination that is a kind of or wherein multiple synergy in organic phosphates heterogeneous ring compound based flame retardants such as poly-(two (phenoxy group) phosphazo alkene).
Further, above-mentioned organic solvent can be ketone class such as acetone, butanone, pimelinketone etc., aromatic hydrocarbons is such as a kind of or wherein multiple combination in benzene, toluene, dimethylbenzene.
The present invention discloses the preparation method of above-mentioned cyanate compositions, first the molecular weight of polyphenylene oxide is reduced by redistribution reaction, simultaneously also at the phenolic hydroxyl group connecting functionalization at polyphenylene oxide molecular chain two ends, the consistency of itself and cyanate ester resin can be increased, also can be used as a class solidifying agent of cyanate ester resin crosslinking curing. The monomer simultaneously adding the good thermoplastic polymer of appropriate dielectric properties is such as vinylbenzene, dicyclopentadiene, cycloolefin and other unsaturated olefin monomer, add a certain amount of environmental protection fire retarding agent again, constitute the copper-clad plate cyanate resin composition that environmental protection flame retardant, dielectric properties and thermal characteristics are good, specific as follows:
1. the redistribution reaction of polyphenylene oxide
Adding the polyphenylene oxide of 100 parts, the dihydroxyphenyl propane of 8��12 parts in four mouthfuls of flasks, then add toluene 150 parts, be heated to 90��100 DEG C, stirring rod stirs until dissolving transparent. Being dissolved in toluene by the benzoyl peroxides of 4 parts, and dropwise drip in reaction vessel, reaction continues 100 minutes. In whole process, always keep nitrogen lead to into. After reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking.
2. the preparation of glue
Choose 25��65 parts of above-mentioned polyphenylene oxide, add the toluene of 35��75 parts, be stirred and heated to 100 DEG C, until it dissolves completely, add the olefinic monomer of 5��135 parts, be stirred to solution equal one. Then the cyanic acid ester of 100 parts is added, the organometallic salt catalysts of 0.05��0.2 part, keep solution temperature to be 97��103 DEG C simultaneously, after all solution all adds, solution temperature is elevated to 105 DEG C, and reacts 5h, obtain the uniform solution containing polyphenylene oxide, olefin polymer and cyanic acid ester composition, then add appropriate solvent and coupling agent, mineral filler and phosphonium flame retardant, after high speed shear, emulsification and standing slaking, obtain preparing the glue liquid of copper-clad plate prepreg.
Present invention also offers a kind of method utilizing said composition to prepare copper-clad plate, specific as follows:
Glasscloth is cut into fixed measure, and immerses in glue, within 4��5 minutes, obtain the prepreg of resin content as 50% taking the condition of 175 DEG C baking in an oven; Get 4��8 aforesaid prepregs, respectively place an electrolytic copper foil on the upper and lower surface of prepreg, put into high temperature press, apply 45kg/cm2Pressure and the temperature of 200 DEG C keep obtaining copper-clad plate in 120 minutes. Using the copper-clad plate prepared by above composition to have good thermal characteristics, dielectric properties, flame retardant properties can reach UL-94V-0 simultaneously.
Further, the above-mentioned electronic isolation material as printed board substrate--cloth is the non-woven fibre being made up of organic and inorganic fiber, and this kind of inorganic fibre has E-glasscloth, D-glasscloth, S-glasscloth, Q-glasscloth etc.; Organic fibre has polyimide, polyester, tetrafluoroethylene etc., can also be that organic mixture with inorganic fibre is made into.
Implement the present invention, there is following useful effect:
The present invention processes through redistribution reaction by introducing, low-molecular polyphenylene ether, solve the shortcoming of macromolecule polyphenylene oxide mobility difference, add the consistency that monomer alkene improves system further simultaneously, and on the dielectric properties of system without obvious impact, said composition can be used for manufacturing high performance copper-clad plate green, environmental protection, and the copper-clad plate of the type has the performance of outstanding dielectric properties, thermotolerance and environmental protection flame retardant.
Embodiment
It is described further to processing step and the outstanding effect thereof of the present invention below.
Embodiment 1
Adding the polyphenylene oxide of 100 parts, the dihydroxyphenyl propane of 9.5 parts in four mouthfuls of flasks, then add toluene 150 parts, be heated to 100 DEG C, stirring rod stirs until dissolving transparent. Being dissolved in toluene by the benzoyl peroxides of 4 parts, and dropwise drip in reaction vessel, reaction continues 100 minutes. In whole process, always keep nitrogen lead to into. After reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking.
Choose 65 parts of above-mentioned polyphenylene oxide, add the toluene of 75 parts, be stirred and heated to 100 DEG C, until it dissolves completely, add the dicyclopentadiene monomer of 35 parts, be stirred to solution equal one. Then the cyanic acid ester of 100 parts is added, the organometallic salt catalysts of 0.12 part, keep solution temperature to be 97��103 DEG C simultaneously, after all solution all adds, solution temperature is elevated to 105 DEG C, and reacts 5h, obtain the uniform solution containing polyphenylene oxide, polydicyclopentadiene and cyanic acid ester composition, then add appropriate solvent and coupling agent, mineral filler and phosphonium flame retardant, after high speed shear, emulsification and standing slaking, obtain preparing the glue liquid of copper-clad plate prepreg.
Embodiment 2
Adding the polyphenylene oxide of 100 parts, the dihydroxyphenyl propane of 9.5 parts in four mouthfuls of flasks, then add toluene 150 parts, be heated to 100 DEG C, stirring rod stirs until dissolving transparent. Being dissolved in toluene by the benzoyl peroxides of 4 parts, and dropwise drip in reaction vessel, reaction continues 100 minutes. In whole process, always keep nitrogen lead to into. After reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking.
Choose 80 parts of above-mentioned polyphenylene oxide, add the toluene of 65 parts, be stirred and heated to 100 DEG C, until it dissolves completely, add the styrene monomer of 20 parts, be stirred to solution equal one. Then the cyanic acid ester of 100 parts is added, the organometallic salt catalysts of 0.08 part, keep solution temperature to be 97��103 DEG C simultaneously, after all solution all adds, solution temperature is elevated to 105 DEG C, and reacts 5h, obtain containing polyphenylene oxide, polystyrene and cyanic acid ester composition uniform solution, then add appropriate solvent and coupling agent, mineral filler and phosphonium flame retardant, after high speed shear, emulsification and standing slaking, obtain preparing the glue liquid of copper-clad plate prepreg.
Embodiment 3
Adding the polyphenylene oxide of 100 parts, the dihydroxyphenyl propane of 9.5 parts in four mouthfuls of flasks, then add toluene 150 parts, be heated to 100 DEG C, stirring rod stirs until dissolving transparent. Being dissolved in toluene by the benzoyl peroxides of 4 parts, and dropwise drip in reaction vessel, reaction continues 100 minutes. In whole process, always keep nitrogen lead to into. After reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking.
Choose 50 parts of above-mentioned polyphenylene oxide, add the toluene of 65 parts, be stirred and heated to 100 DEG C, until it dissolves completely, add the styrene monomer of 100 parts, be stirred to solution equal one. Then the cyanic acid ester of 100 parts is added, the organometallic salt catalysts of 0.12 part, keep solution temperature to be 97��103 DEG C simultaneously, after all solution all adds, solution temperature is elevated to 105 DEG C, and reacts 5h, obtain containing polyphenylene oxide, polystyrene and cyanic acid ester composition uniform solution, then add appropriate solvent and coupling agent, mineral filler and phosphonium flame retardant, after high speed shear, emulsification and standing slaking, obtain preparing the glue liquid of copper-clad plate prepreg.
Comparative example 1:
Adding the polyphenylene oxide of 100 parts, the dihydroxyphenyl propane of 2 parts in four mouthfuls of flasks, then add toluene 60 parts, be heated to 100 DEG C, stirring rod stirs until dissolving transparent. Being dissolved in toluene by the benzoyl peroxides of 4 parts, and dropwise drip in reaction vessel, reaction continues about 100 minutes. In whole process, nitrogen one lead directly to into. After reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking.
Choose 50 parts of above-mentioned polyphenylene oxide, add the toluene of 65 parts, it is stirred and heated to 100 DEG C, until it dissolves completely, then adds the cyanic acid ester of 100 parts, the organometallic salt catalysts of 0.12 part, keep solution temperature to be 97��103 DEG C simultaneously, after all solution all adds, solution temperature is elevated to 105 DEG C, and react 5h, obtain containing polyphenylene oxide and cyanic acid ester composition polymer composition. Then add appropriate solvent and coupling agent, mineral filler and phosphonium flame retardant, after high speed shear, emulsification and standing slaking, obtain preparing the glue liquid of copper-clad plate prepreg.
Comparative example 2:
Adding the polyphenylene oxide of 100 parts, the dihydroxyphenyl propane of 8 parts in four mouthfuls of flasks, then add toluene 150 parts, be heated to 100 DEG C, stirring rod stirs until dissolving completely. Being dissolved in toluene by the benzoyl peroxides of 4 parts, and dropwise drip in reaction vessel, reaction continues about 100 minutes. In whole process, nitrogen one lead directly to into. After reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking.
Choose the polydicyclopentadiene of 35 parts of above-mentioned polyphenylene oxide and 15 parts, add the toluene of 65 parts, it is stirred and heated to 100 DEG C, until it dissolves completely, then adds the cyanic acid ester of 100 parts, the organometallic salt catalysts of 0.12 part, keep solution temperature to be 97��103 DEG C simultaneously, after all solution all adds, solution temperature is elevated to 105 DEG C, and react 5h, obtain the polymer composition being made up of polyphenylene oxide, polydicyclopentadiene and cyanic acid ester. Then add appropriate solvent and coupling agent, mineral filler and phosphonium flame retardant, after high speed shear, emulsification and standing slaking, obtain preparing the glue liquid of copper-clad plate prepreg. Following table is the test result of the copper-clad plate adopting the present invention to obtain
Sheet material test result
Claims (8)
1. a cyanate compositions, it is characterised in that, said composition comprises following component by weight:
Cyanic acid ester 100 parts
Low-molecular polyphenylene ether 25��65 parts
Olefinic monomer 5��135 parts
Organometallic salt catalysts 0.05��0.2 part, and
Mineral filler, environmental protection fire retarding agent and organic solvent;
Described low-molecular polyphenylene ether is the product that polyphenylene oxide obtains through redistribution reaction;
Described redistribution reaction step comprises: (a) adds the polyphenylene oxide of 100 parts, the dihydroxyphenyl propane of 8��12 parts in four mouthfuls of flasks, then adds toluene 150 parts, is heated to 90��100 DEG C, and stirring rod stirs until dissolving transparent;
B the benzoyl peroxide of 4 parts is dissolved in toluene by (), and dropwise drip in reaction vessel, and reaction continues 100 minutes;
(c) in whole process, always keep nitrogen lead to into, after reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking.
2. cyanate compositions as claimed in claim 1, it is characterized in that, described cyanic acid ester is the combination of one or two or more kinds in bisphenol A cyanate ester, bisphenol E-type cyanate, bisphenol-f type cyanic acid ester, bis-phenol M type cyanic acid ester, tetramethyl-bisphenol-f type cyanic acid ester, dicyclopentadiene bisphenol A cyanate ester.
3. cyanate compositions as claimed in claim 1, it is characterized in that, the combination of one or two or more kinds that described organometallic salt catalysts is selected from isocaprylic acid zinc, cobalt iso-octoate, isocaprylic acid chromium, acetylacetone cobalt, zinc acetylacetonate, acetylacetone copper, ferric acetyl acetonade, manganese acetylacetonate, cobalt naphthenate, zinc naphthenate, naphthenic acid titanium or manganese naphthenate.
4. cyanate compositions as claimed in claim 1, it is characterized in that, described mineral filler is selected from aluminium hydroxide, magnesium hydroxide, silicon-dioxide, hollow glass micropearl, mica, clay, talcum powder, kaolin, aluminum oxide, titanium oxide, beryllium oxide, silicon nitride, boron nitride, barium sulfate, barium titanate, strontium titanate, calcium titanate, pure aluminium silicate, Calucium Silicate powder, Magnesium Silicate q-agent or aluminum borate.
5. cyanate compositions as claimed in claim 1, it is characterized in that, described fire retardant is triphenylphosphate, Tritolyl Phosphate, trioctyl phosphate, diphenyl octyl phosphate, phosphate diphenyl isodecyl ester, tricresyl phosphate (dimethylbenzene) ester, phosphoric acid hexichol trimethylphenylmethane ester, phosphoric acid hexichol isopropyl phenyl ester, Resorcinol two [two (2, 6-3,5-dimethylphenyl) phosphoric acid ester], diphenyl 2 ethylhexyl phosphate, or methylethyl phospho acid aluminium, aluminum diethylphosphinate, hydroxymethyl phenyl phospho acid aluminium, or 3-hydroxy phenyl phosphorus acyl propionic acid, hydroxyl phenylphosphorous acid propionic acid, hydroxy-propionic acid base phenylphosphorous acid, 2-carboxy ethyl (phenyl) phospho acid or 9, 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound (DOPO), the combination of one or two or more kinds in poly-(two (phenoxy group) phosphazo alkene).
6. cyanate compositions as claimed in claim 1, it is characterised in that, described organic solvent is selected from acetone, butanone or pimelinketone and comprises the combination of a kind of in benzene, toluene, dimethylbenzene or two kinds.
7. one kind utilizes the method that the cyanate compositions described in claim 1 prepares copper-clad plate, it is characterised in that, comprise the following steps:
(1) redistribution reaction of polyphenylene oxide
A () adds the polyphenylene oxide of 100 parts, the classification properties-correcting agent of 8��12 parts in four mouthfuls of flasks, then add toluene 150 parts, is heated to 90��100 DEG C, and stirring rod stirs until dissolving transparent;
B the initiator of 4 parts is dissolved in toluene by (), and dropwise drip in reaction vessel, and reaction continues 100 minutes;
(c) in whole process, always keep nitrogen lead to into, after reaction terminates, product methanol extraction also filters, and obtains the low-molecular polyphenylene ether through phenolic hydroxyl group end-blocking;
(2) preparation of glue
A () chooses 25��65 parts of above-mentioned polyphenylene oxide, add the toluene of 35��75 parts, is stirred and heated to 100 DEG C, until it dissolves completely;
B () adds the olefinic monomer of 5��135 parts, be stirred to solution equal one;
C () adds the cyanic acid ester of 100 parts, the organometallic salt catalysts of 0.05��0.2 part, keeps solution temperature to be 97��103 DEG C simultaneously;
D solution temperature is elevated to 105 DEG C by (), and react 5h, obtains the uniform solution containing polyphenylene oxide, olefin polymer and cyanic acid ester composition;
E () adds appropriate solvent and coupling agent, mineral filler and phosphonium flame retardant;
Obtain preparing the glue liquid of copper-clad plate prepreg after (f) high speed shear, emulsification and standing slaking;
(3) preparation of copper-clad plate
A glasscloth is cut into fixed measure by (), and immerse in the obtained glue liquid of step (2);
B () baking box obtains the prepreg of resin content as 50% for 4��5 minutes taking the condition of 150 DEG C��180 DEG C baking;
C () gets 4��8 aforesaid prepregs, respectively place an electrolytic copper foil on the upper and lower surface of prepreg, puts into high temperature press and keeps obtaining copper-clad plate in 100��130 minutes;
Described polyphenylene oxide redistribution reaction classification properties-correcting agent is 2,6-dimethyl-4-methoxyphenol, 2,6-dimethyl-4-methylphenol, 4-methoxyphenol, 4-TBP, 4-methylphenol, 4-ethylphenol, dihydroxyphenyl propane, 4-nonyl phenol, Pentaphen, one or more combination to tert-octylphenol, 4-cumylphenol, phenol, cresols, in xylenol, Resorcinol, pyrogallol; Described polyphenylene oxide redistribution reaction initiator is t-butylperoxyisopropyl carbonic ether, 1, two (oxygen base crossed by tertiary own base)-3 of 1-, 3,5-trimethyl-cyclohexane, 1,1-two (t-butylperoxy)-2-methylcyclohexane, tert-butyl hydroperoxide benzoate, dicumyl peroxide, di-t-butyl peroxide, cumyl hydroperoxide, 3,3'5, one or more combination in 5'-tetramethyl--4,4'-diphenoquinone, Diisopropyl azodicarboxylate, benzoyl peroxide.
8. method as claimed in claim 7, it is characterised in that, the pressure that during preparation copper-clad plate, described high temperature press applies is 45kg/cm2, temperature is 200 DEG C.
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| CN102382382A (en) * | 2010-08-12 | 2012-03-21 | 日立电线株式会社 | Thermoplastic resin composition, adhesive film and wiring film using the same |
| CN102719096A (en) * | 2012-06-20 | 2012-10-10 | 广东汕头超声电子股份有限公司覆铜板厂 | Resin composition and preparation method thereof |
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| CN103467982A (en) | 2013-12-25 |
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Effective date of registration: 20230110 Address after: No. 28, Guangshun Road, Haojiang District, Shantou City, Guangdong Province, 515000 Patentee after: Shantou Ultrasonic Copper Clad Plate Technology Co.,Ltd. Address before: 515000 Plot E04, Haojiang Free Trade Zone, Shantou City, Guangdong Province Patentee before: GUANGDONG SHANTOU ULTRASONIC ELECTRONIC CO.,LTD. COPPER CLAD FACTORY |
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