CN103182831B - A kind of preparation technology of the copper-clad laminate based on halogen-free flame-retardant resin constituent - Google Patents
A kind of preparation technology of the copper-clad laminate based on halogen-free flame-retardant resin constituent Download PDFInfo
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Abstract
A kind of preparation technology of the copper-clad laminate based on halogen-free flame-retardant resin constituent, first carry out the making of fabric glue, carry out the making of glue A again, then glue liquid B making is carried out, re-use 7628 or 2116 glass cloth dipping fabric glues, and in an oven except desolventizing is prepared into fabric prepreg, wood pulp paper is used to flood glue A successively, glue liquid B, toast in an oven, be prepared into core material prepreg, finally by 1-12 sheet core material prepreg, a fabric prepreg is respectively pasted on two sides, one or both sides paste an electrolytic copper foil, superimposed good after, hot-forming, the copper-clad laminate made, there is agent of low hygroscopicity, high-fire resistance, high reliability, high CTI, halogen-free flame-retardance, and there is excellent processability, be applicable to unleaded requirement.
Description
Technical field
The present invention relates to electronic material copper-clad plate and manufacture processing technique field, be specifically related to a kind of preparation technology of the copper-clad laminate based on halogen-free flame-retardant resin constituent.
Background technology
The copper-clad plate of CEM-1 type is that epoxy resin-impregnated glue makes fabric and core material respectively, then forms through hot pressing coated with Copper Foil by glass-fiber-fabric and bleached wood pulp paper as enhancing base material.There is excellent heat resistance, lower water absorption rate, excellent machining property and good electric insulating quality and mechanical strength, there is the characteristic that the low cost performance of cost is high, be mainly applicable to the aspects such as OA equipment, power supply board, LCDTV, game machine, household electrical appliance.But traditional printed circuit copper-clad laminate, the main halogen that uses is fire-retardant.These materials can produce many poisonous and hazardous carcinogens when burning.Along with the degree of concern of the mankind to environmental protection is more and more higher, cause one research and development at PCB industry and produce the upsurge of halogen-free flame-retardance printed circuit with multiple copper-clad laminate thus.
-straight since, CEM-1 type copper-clad laminate, realizing halogen-free flameproof Major Technology adopts phosphorous based epoxy resin as main body, adopt dicyandiamide, phenolic resins as curing agent, again in formula system, the fire retardant adding the inorganic filler such as aluminium hydroxide or magnesium hydroxide and phosphoric acid ester realizes the requirement of halogen-free flameproof.But, the special construction of limited P=O base with phosphorous epoxy resin and in the fire retardant matter of phosphoric acid ester, cause filling a prescription and there is stronger hygroscopicity and water-disintegrable, therefore the introducing of this kind of material in formula, make under highly basic or hot and humid condition (as in PCB processing and making process), very easily because producing layering plate bursting phenomenon, have a strong impact on the service life of sheet material and manufactured goods.In addition, the existence of the material of these easy moisture absorptions, the reduction in electric equipment service life that also can cause producing with copper-clad laminate.
And at present for solving large, the explosive plate problem of hygroscopicity of halogen-free board, adopt the fire retardant (see in patent CN102020230A) of phosphonitrile class, because of the particularity of its chemical constitution, P atom is coated in the middle of other atoms, greatly reduces the moisture pick-up properties of fire retardant.But, this application is for reaching fire resistance, use a large amount of phenoxy phosphazene fire retardant to combine containing N class phenolic resins and phosphate, because phenoxy phosphazene fire retardant addition is greatly easily separated out, melamine modified phenolic resin, phosphoric acid ester solidfied material heat-resisting low, water imbibition is larger.Cause sheet material to be also short of to some extent in heat resistance and the aspect of performance of resistance to the moisture absorption, particularly can not meet that current pb-free solder requires, the sheet material resting period is short.And the product that the present invention develops, can address these problems further, meanwhile, cost is low, performance is more excellent, the Halogen of CEM-1 sheet material, unleaded requirement can be met.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparation technology of the copper-clad laminate based on halogen-free flame-retardant resin constituent, the copper-clad laminate made, there is agent of low hygroscopicity, high-fire resistance, high reliability, high CTI, halogen-free flame-retardance and have excellent processability, be applicable to unleaded requirement.
In order to achieve the above object, the technical scheme that the present invention takes is:
Based on a preparation technology for the copper-clad laminate of halogen-free flame-retardant resin constituent, comprise the following steps:
1) making of fabric glue: with weight parts, by first ring epoxy resins 40-90 part, second epoxy resin 8-60 part, dicyandiamide 1-6 part, phosphazene flame retardant 0-30 part, inorganic filler 10-80 part, imidazoles curing accelerator 0.01-1.0 part and organic solvent 35-80 part, the glue be modulated into;
2) making of glue A: by water-soluble resin 50-100 part, phosphazene flame retardant 20-80 part and acetone 400-900 part and water 10-100 part, be modulated into glue;
3) making of glue liquid B: by first ring epoxy resins 20-70 part, second epoxy resin 8-30 part, phosphorous epoxy resin 0-50 part, phenolic resins or modified phenolic class curing agent 15-68 part, phosphazene flame retardant 5-40 part, inorganic filler 20-150 part, curing accelerator 0.01-2.0 part and organic solvent 60-130 part, be modulated into glue;
4) 7628 or 2116 glass cloth dipping fabric glues are used, and in an oven in 175 DEG C of baking 2-8min, except desolventizing is prepared into fabric prepreg, use wood pulp paper to flood glue A, glue liquid B successively, in an oven in 175 DEG C of baking 2-7min, be prepared into core material prepreg;
5) by 1-12 sheet core material prepreg, a fabric prepreg is respectively pasted on two sides, and one or both sides paste an electrolytic copper foil, superimposed good after, at temperature 90-200 DEG C, pressure 10-100Kg/cm
2lower hot-forming.
Described first ring epoxy resins is difunctional halogen-free epoxy resin, namely the halogen-free epoxy resin containing 2 epoxide groups in a molecule, comprises one or more mixing of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin or alicyclic based epoxy resin;
The second described epoxy resin is epoxy resins of phenol formaldehyde type, dicyclopentadiene type epoxy resin, aralkylphenol type epoxy resin, one or more mixing containing naphthalene nucleus class polyfunctional epoxy resin, anthracycline polyfunctional epoxy resin or glycidyl amine type epoxy resin;
Described phosphorous epoxy resin is phosphate modified phosphorous epoxy resin, DOPO modification phosphorous epoxy resin or DOPO-HQ modification phosphorous epoxy resin;
Described phosphazene flame retardant refers to phenoxy group group of polyphosphazenes fire retardant, and its structural formula is as follows:
Wherein, n is the integral multiple of 3-15, and R is H ,-OH ,-NH
2,-CN, epoxy radicals, and the gross weight of phosphate anion in phosphazene compound and orthophosphite ions is no more than 500ppm; Above fire retardant can be used alone or two or more used in combination, these groups can with the hydroxyl effect in wood pulp paper, reduce the surface hydroxyl in wood pulp paper, have reactivity with the epoxy reaction in resin, thus can effectively improve the precipitation phenomenon of fire retardant simultaneously.
Described phenolic resins or modified phenolic class curing agent are linear phenolic resin curing agent, dry oil modified phenolic resin and benzoxazine colophony, above resin is used alone or mixed use of two or more, wherein, linear phenolic resin comprise phenol Linear phenolic resins, ortho-cresol novolac resin, bisphenol A phenolic resin, dicyclopentadiene type phenolic resins, containing naphthalene nucleus or aralkylphenol type phenolic resins; Dry oil modified phenolic resin comprises tung oil modified phenolic resin, Cardanol Modified PF Resin, nonyl phenol phenol-formaldehyde resin modified or castor oil modified phenolic resins; Benzoxazine colophony refers to monocycle aniline type benzoxazine, diaminodiphenyl-methane type benzoxazine, bisphenol A-type benzoxazine colophony, bisphenol-f type benzoxazine colophony, bisphenol S type benzoxazine colophony, epoxide modified benzoxazine colophony.
Described water-soluble resin refers to have hydrophilic Small molecular resin, its molecular weight is at 100-3000, and containing hydroxyl, amino polar group, comprise water-soluble epoxy resin, water soluble phenol resin, water-soluble polyester resin, water soluble acrylic resin, water miscible abietic resin or watersoluble melamine modified resin, above resin is used alone or mixed use of two or more.
Described inorganic filler is kaolin, hydrotalcite, aluminium hydroxide, boehmite, magnesium hydroxide, Firebrake ZB, glass dust, imvite, titanium oxide, aluminium oxide, aluminium nitride, magnesia, calcium carbonate, silicon powder or mica powder powder, and the interpolation of filler is that above one or more are used in combination.
Described curing accelerator comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, metal-organic complex or glyoxaline compounds, the use of curing accelerator selects one or more used in combination, the consumption of curing accelerator is the 0.01-5.0wt% of resin, the gelation time of glue liquid B should lower than 100s, described tertiary amine is specially triethylamine, tri-butylamine, dimethyl amine ethanol, N, N-dimethyl-aminomethyl phenol; Described three grades of phosphines are specially triphenylphosphine, tetrabutyl phosphonium bromide phosphine, tetrabutylammonium iodide phosphine, butyl triphenyl phosphonium iodide, butyltriphenylphosphonium bromide phosphine, butyltriphenylphosphonium chloride phosphine; Described quaternary ammonium salt is specially 4 bromide, benzyltrimethylammonium chloride; Described metal-organic complex is specially zinc acetate, Schweinfurt green; Described glyoxaline compound is specially glyoxal ethyline, 2-ethyl-4 methylimidazole, 2-phenylimidazole, 2-phenyl-4 methylimidazole, 1-1-cyanoethyl-2-methylimidazole.
Organic solvent used comprises acetone, butanone, methyl alcohol, alcohol, toluene, dimethylbenzene, DMF, glycol monoethyl ether, propylene glycol monomethyl ether, ethyl acetate, cyclohexanone, and above-mentioned organic solvent is used alone or mixed use of two or more.
Halogen-free flame-retardant resin constituent of the present invention compared with prior art, has lower resistance to hygroscopicity, higher heat resistance and high CTI performance; 2, adopt the phosphonitrile fire retardant of solubility and water-soluble resin to carry out pretreatment to wood pulp paper in advance in core material of the present invention, effectively raise the fire resistance of sheet material, heat resistance, resistance to water and punching processing; 3, the use of phenolic resins or modified phenolic class curing agent makes sheet material have agent of low hygroscopicity, high-fire resistance, high reliability and have excellent processability, be conducive to lifting system processability and easily by the test of pb-free solder technique.4, the phosphorus in system in the introducing of nitrogen element and system is reached synergy, is beneficial to the lifting of anti-flammability.Therefore, the prepreg that halogen-free flame-retardant resin constituent of the present invention makes and copper-clad laminate, have agent of low hygroscopicity, high-fire resistance, high reliability, high CTI, halogen-free flame-retardance and have excellent processability, be applicable to unleaded requirement.
Detailed description of the invention
Following examples illustrate explanation of the present invention each embodiment of the present invention.But these embodiments not limiting the present invention in any way.
Embodiment 1
Based on a preparation technology for the copper-clad laminate of halogen-free flame-retardant resin constituent, comprise the following steps:
1) making of fabric glue: bisphenol A epoxide resin 70 parts, Study On O-cresol Epoxy Resin 30 parts, dicyandiamide 2.8 parts, phenol oxygen base tripolyphosphazene 30 parts, boehmite 35 parts, 2-ethyl-4 methylimidazole 0.2 part and DMF95 part, be modulated into glue;
2) making of glue A: water soluble phenol resin 20 parts, phenol oxygen base tripolyphosphazene 80 parts and 750 parts, acetone and 80 parts, water, be modulated into glue;
3) making of glue liquid B: bisphenol A epoxide resin 30 parts, Study On O-cresol Epoxy Resin 20 parts, phosphorous epoxy resin 50 parts, bisphenol-f type benzoxazine colophony 25 parts, Cardanol Modified PF Resin 10 parts, phenoxy group tripolyphosphazene 5 parts, 100 parts, aluminium hydroxide, 2-ethyl-4 methylimidazole 0.2 part and 105 parts, acetone, be modulated into glue;
4) 7628 glass cloth dipping fabric glues are used, and toast (oven temperature 175 DEG C) 2-8min in an oven, except desolventizing is prepared into fabric prepreg, use wood pulp paper to flood glue A, glue liquid B successively, toast (oven temperature 175 DEG C) 2-7min in an oven and be prepared into core material prepreg;
5) by 5 core material prepregs, a fabric prepreg is respectively pasted on two sides, and one or both sides paste an electrolytic copper foil, superimposed good after, at temperature 90-200 DEG C, pressure 10-100Kg/cm
2lower hot-forming.Respective performances is in table one.
Embodiment 2
1) making of fabric glue: bisphenol A epoxide resin 70 parts, Study On O-cresol Epoxy Resin 30 parts, dicyandiamide 2.8 parts, phenol oxygen base tripolyphosphazene 30 parts, boehmite 30 parts, 2-ethyl-4 methylimidazole 0.1 part and DMF90 part, be modulated into glue;
2) making of glue A: water soluble phenol resin 20 parts, phenol oxygen base tripolyphosphazene 80 parts and 750 parts, acetone and 80 parts, water, be modulated into glue;
3) making of glue liquid B: bisphenol A epoxide resin 70 parts, Study On O-cresol Epoxy Resin 30 parts, bisphenol-f type benzoxazine colophony 25 parts, Cardanol Modified PF Resin 10 parts, phenoxy group tripolyphosphazene 35 parts, 70 parts, aluminium hydroxide, 2-ethyl-4 methylimidazole 0.2 part and 105 parts, acetone, be modulated into glue;
4) 7628 glass cloth dipping fabric glues are used, and toast (oven temperature 175 DEG C) 2-8min in an oven, except desolventizing is prepared into fabric prepreg, use wood pulp paper to flood glue A, glue liquid B successively, toast (oven temperature 175 DEG C) 2-7min in an oven and be prepared into core material prepreg;
5) by 5 core material prepregs, a fabric prepreg is respectively pasted on two sides, and one or both sides paste an electrolytic copper foil, superimposed good after, at temperature 90-200 DEG C, pressure 10-100Kg/cm
2lower hot-forming.Respective performances is in table one.
Embodiment 3
1) making of fabric glue: bisphenol A epoxide resin 60 parts, Study On O-cresol Epoxy Resin 40 parts, dicyandiamide 2.8 parts, phenol oxygen base tripolyphosphazene 15 parts, boehmite 35 parts, 2-ethyl-4 methylimidazole 0.3 part and DMF88 part, be modulated into glue;
2) making of glue A: water soluble phenol resin 50 parts, phenol oxygen base tripolyphosphazene 50 parts and 750 parts, acetone and 80 parts, water, be modulated into glue;
3) making of glue liquid B: bisphenol A epoxide resin 40 parts, Study On O-cresol Epoxy Resin 20 parts, phosphorous epoxy resin 40 parts, bisphenol-f type benzoxazine colophony 35 parts, tung oil modified phenolic resin 20 parts, phenoxy group tripolyphosphazene 30 parts, 70 parts, aluminium hydroxide, 2-ethyl-4 methylimidazole 0.2 part and 105 parts, acetone, be modulated into glue;
4) 7628 glass cloth dipping fabric glues are used, and toast (oven temperature 175 DEG C) 2-8min in an oven, except desolventizing is prepared into fabric prepreg, use wood pulp paper to flood glue A, glue liquid B successively, toast (oven temperature 175 DEG C) 2-7min in an oven and be prepared into core material prepreg;
5) by 5 core material prepregs, a fabric prepreg is respectively pasted on two sides, and one or both sides paste an electrolytic copper foil, superimposed good after, at temperature 90-200C, pressure 10-100Kg/cm
2lower hot-forming.Respective performances is in table one.
Comparative example 1:
1) making of fabric glue: bisphenol A type epoxy resin 50 parts, phosphorous epoxy resin 50 parts, dicyandiamide 4.2 parts, 30 parts, aluminium hydroxide, 2-ethyl-4 methylimidazole 0.2 and DMF85 part, modulation glue;
2) core material glue: bisphenol A type epoxy resin 50 parts, phosphorous epoxy resin 50 parts, linear phenolic resin 20 parts, phenoxy group tripolyphosphazene 50 parts, 70 parts, aluminium hydroxide, 2-ethyl-4 methylimidazole 0.18 part and 105 parts, acetone, modulation glue glue;
3) use 7628 glass cloth dipping fabric glues, and toast (oven temperature 175 DEG C) 2-8min in an oven, except desolventizing is prepared into fabric prepreg.Use wood pulp paper dipping core material glue, dry (oven temperature 175 DEG C) 2-8min is prepared into core material prepreg in an oven.
4) by 5 core material prepregs, a fabric prepreg is respectively pasted on two sides, and one or both sides paste an electrolytic copper foil, superimposed good after, at temperature 90-200C, pressure 10-100Kg/cm
2lower hot-forming.Respective performances is in table one.
Comparative example 2:
1) making of fabric glue: bisphenol A type epoxy resin 50 parts, phosphorous epoxy resin 50 parts, dicyandiamide 4.2 parts, 30 parts, aluminium hydroxide, phenoxy group tripolyphosphazene 20 parts, 2-ethyl-4 methylimidazole 0.2 and DMF95 part, modulation glue;
2) core material glue
:bisphenol A type epoxy resin 50 parts, phosphorous epoxy resin 50 parts, linear phenolic resin 8 parts, tung oil modified phenolic resin 30 parts, phenoxy group tripolyphosphazene 20 parts, triphenyl phosphoric acid ester 30 parts, 50 parts, aluminium hydroxide, 2-imidazoles 0.8 part and 100 parts, acetone, modulation glue;
3) use 7628 glass cloth dipping fabric glues, and toast (oven temperature 175 DEG C) 2-8min in an oven, except desolventizing is prepared into fabric prepreg.Use wood pulp paper dipping core material glue, dry (oven temperature 175 DEG C) 2-8min is prepared into core material prepreg in an oven.
4) by 5 core material prepregs, a fabric prepreg is respectively pasted on two sides, and one or both sides paste an electrolytic copper foil, superimposed good after, at temperature 90-200C, pressure 10-100Kg/cm
2lower hot-forming.Respective performances is in table one.
* processability grade: ◎ excellent, zero good, △ normal, × bad
Results contrast is analyzed:
As can be seen from the above results, halogen-free fire-proof resin composition of the present invention, there is high creepage trace characteristic, with the sheet material that it is prepared, there is agent of low hygroscopicity, high-fire resistance, high reliability, high CTI, halogen-free flame-retardance and have excellent processability, and the heat-resisting 20s of being greater than, T260 are greater than 1min after Td > 300 DEG C, PCT, meet and unleadedly require index, be applicable to unleaded requirement.In addition, also there is the features such as storage period is long, manageable and easy to use, and be applicable to make the single double side printed wiring board requiring CTI >=600V.
Claims (6)
1. based on a preparation technology for the copper-clad laminate of halogen-free flame-retardant resin constituent, it is characterized in that, comprise the following steps:
1) making of fabric glue: with weight parts, by first ring epoxy resins 40-90 part, second epoxy resin 8-60 part, dicyandiamide 1-6 part, phosphazene flame retardant 0-30 part, inorganic filler 10-80 part, imidazoles curing accelerator 0.01-1.0 part and organic solvent 35-80 part, the glue be modulated into;
2) making of glue A: by water-soluble resin 50-100 part, phosphazene flame retardant 20-80 part and acetone 400-900 part and water 10-100 part, be modulated into glue;
3) making of glue liquid B: by first ring epoxy resins 20-70 part, second epoxy resin 8-30 part, phosphorous epoxy resin 0-50 part, phenolic resins or modified phenolic class curing agent 15-68 part, phosphazene flame retardant 5-40 part, inorganic filler 20-150 part, curing accelerator 0.01-2.0 part and organic solvent 60-130 part, be modulated into glue;
Described first ring epoxy resins is difunctional halogen-free epoxy resin, namely the halogen-free epoxy resin containing 2 epoxide groups in a molecule, comprises one or more mixing of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, biphenyl type epoxy resin or alicyclic based epoxy resin;
The second described epoxy resin is epoxy resins of phenol formaldehyde type, dicyclopentadiene type epoxy resin, aralkylphenol type epoxy resin, one or more mixing containing naphthalene nucleus class polyfunctional epoxy resin, anthracycline-containing polyfunctional epoxy resin or glycidyl amine type epoxy resin;
Described phosphorous epoxy resin is phosphate modified phosphorous epoxy resin, DOPO modification phosphorous epoxy resin or DOPO-HQ modification phosphorous epoxy resin;
Described phosphazene flame retardant refers to phenoxy group group of polyphosphazenes fire retardant, and its structural formula is as follows:
Wherein, n is the integral multiple of 3-15, and R is H ,-OH ,-NH
2,-CN, epoxy radicals, and the gross weight of phosphate anion in phosphazene compound and orthophosphite ions is no more than 500ppm; Above fire retardant can be used alone or two or more used in combination, these groups can with the hydroxyl effect in wood pulp paper, reduce the surface hydroxyl in wood pulp paper, have reactivity with the epoxy reaction in resin, thus can effectively improve the precipitation phenomenon of fire retardant simultaneously;
4) 7628 or 2116 glass cloth dipping fabric glues are used, and in an oven in 175 DEG C of baking 2-8min, except desolventizing is prepared into fabric prepreg, use wood pulp paper to flood glue A, glue liquid B successively, in an oven in 175 DEG C of baking 2-7min, be prepared into core material prepreg;
5) by 1-12 sheet core material prepreg, a fabric prepreg is respectively pasted on two sides, and one or both sides paste an electrolytic copper foil, superimposed good after, at temperature 90-200 DEG C, pressure 10-100Kg/cm
2lower hot-forming.
2. the preparation technology of a kind of copper-clad laminate based on halogen-free flame-retardant resin constituent according to claim 1, it is characterized in that: described phenolic resins or modified phenolic class curing agent are linear phenolic resin curing agent, dry oil modified phenolic resin and benzoxazine colophony, above resin is used alone or mixed use of two or more, wherein, linear phenolic resin comprise phenol Linear phenolic resins, ortho-cresol novolac resin, bisphenol A phenolic resin, dicyclopentadiene type phenolic resins, containing naphthalene nucleus or aralkylphenol type phenolic resins; Dry oil modified phenolic resin comprises tung oil modified phenolic resin, Cardanol Modified PF Resin, nonyl phenol phenol-formaldehyde resin modified or castor oil modified phenolic resins; Benzoxazine colophony refers to monocycle aniline type benzoxazine, diaminodiphenyl-methane type benzoxazine, bisphenol A-type benzoxazine colophony, bisphenol-f type benzoxazine colophony, bisphenol S type benzoxazine colophony, epoxide modified benzoxazine colophony.
3. the preparation technology of a kind of copper-clad laminate based on halogen-free flame-retardant resin constituent according to claim 1, it is characterized in that: described water-soluble resin refers to have hydrophilic Small molecular resin, its molecular weight is at 100-3000, and containing hydroxyl, amino polar group, comprise water-soluble epoxy resin, water soluble phenol resin, water-soluble polyester resin, water soluble acrylic resin, water miscible abietic resin or watersoluble melamine modified resin, above resin is used alone or mixed use of two or more.
4. the preparation technology of a kind of copper-clad laminate based on halogen-free flame-retardant resin constituent according to claim 1, it is characterized in that: described inorganic filler is kaolin, hydrotalcite, aluminium hydroxide, boehmite, magnesium hydroxide, Firebrake ZB, glass dust, imvite, titanium oxide, aluminium oxide, aluminium nitride, magnesia, calcium carbonate, silicon powder or mica powder powder, the interpolation of filler is that above one or more are used in combination.
5. the preparation technology of a kind of copper-clad laminate based on halogen-free flame-retardant resin constituent according to claim 1, it is characterized in that: described curing accelerator comprises tertiary amine, three grades of phosphines, quaternary ammonium salt, metal-organic complex or glyoxaline compounds, the use of curing accelerator selects one or more used in combination, the consumption of curing accelerator is the 0.01-5.0wt% of resin, the gelation time of glue liquid B should lower than 100s, described tertiary amine is specially triethylamine, tri-butylamine, dimethyl amine ethanol, N, N-dimethyl-aminomethyl phenol; Described three grades of phosphines are specially triphenylphosphine, tetrabutyl phosphonium bromide phosphine, tetrabutylammonium iodide phosphine, butyl triphenyl phosphonium iodide, butyltriphenylphosphonium bromide phosphine, butyltriphenylphosphonium chloride phosphine; Described quaternary ammonium salt is specially 4 bromide, benzyltrimethylammonium chloride; Described metal-organic complex is specially zinc acetate, Schweinfurt green; Described glyoxaline compound is specially glyoxal ethyline, 2-ethyl-4 methylimidazole, 2-phenylimidazole, 2-phenyl-4 methylimidazole, 1-1-cyanoethyl-2-methylimidazole.
6. the preparation technology of a kind of copper-clad laminate based on halogen-free flame-retardant resin constituent according to claim 1, it is characterized in that: organic solvent used comprises acetone, butanone, methyl alcohol, alcohol, toluene, dimethylbenzene, N, dinethylformamide, glycol monoethyl ether, propylene glycol monomethyl ether, ethyl acetate, cyclohexanone, above-mentioned organic solvent is used alone or mixed use of two or more.
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