CN101381506B - Halogen and phosphor-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby - Google Patents
Halogen and phosphor-free flame-proof epoxy resin composition and bonding sheet and copper clad laminate prepared thereby Download PDFInfo
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- CN101381506B CN101381506B CN200810216392XA CN200810216392A CN101381506B CN 101381506 B CN101381506 B CN 101381506B CN 200810216392X A CN200810216392X A CN 200810216392XA CN 200810216392 A CN200810216392 A CN 200810216392A CN 101381506 B CN101381506 B CN 101381506B
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Abstract
The invention relates to a halogen-free non-phosphate fire-retardant epoxy resin composition and a bonding sheet and a copper-clad laminate which are manufactured by the same. The resin composition consists of compositions and a solvent, wherein the compositions comprise biphenyl epoxy resin, a composite curing agent and filler; and the composite curing agent consists of benzoxazine resin, azotic phenol-formaldehyde resin and diaminodiphenylsulfone. The copper-clad laminate which is manufactured by the resin composition comprises a laminate and metal foils which are covered on one side or both sides of the laminate, wherein the laminate comprises a plurality of adhered bonding sheets which are manufactured by the halogen-free non-phosphate fire-retardant epoxy resin composition. The resin composition does not contain halogen and phosphor element, and the fire resistance reaches UL94V-0 level; and the bonding sheet and the copper-clad laminate which are manufactured by the resin composition have high heat resistance, high reliability, high glass-transition temperature, flame retardancy, low water absorption rate, low dielectric loss, low thermal expansion coefficient and good processability.
Description
Technical field
The present invention relates to a kind of composition epoxy resin and, relate in particular to a kind of halogen and phosphor-free flame-proof epoxy resin composition with the bonding sheet and the copper-clad laminate of its making, and with the printed electronic circuit of its making with bonding sheet and copper-clad laminate.
Background technology
Traditional printed electronic circuit is used copper-clad laminate, mainly adopts brominated epoxy resin, realizes the anti-flaming function of sheet material through bromine.But in recent years, in the products of combustion of the waste electrical and electronic equipment of halogens such as brominated, chlorine, check out carcinogenic substances such as dioxin, diphenylene-oxide, and the Halogen product might discharge the highly toxic substance hydrogen halide in combustion processes.On July 1st, 2006, two parts of environmental protection instructions of European Union " about scrapping the electric/electronic device instruction " and " ROHS " formal enforcement.The enforcement of these two parts of instructions makes the exploitation of halogen-free flameproof copper-clad laminate become the focus of industry, and the producer of each copper-clad laminate all releases the halogen-free flameproof copper-clad laminate of oneself one after another.
At present, the major technique approach of realization copper-clad laminate halogen-free flameproof has two kinds, first kind of approach; The employing phosphorous epoxy resin is a matrix resin; Adopting Dyhard RU 100 or resol then is solidifying agent, adds mineral fillers such as a certain amount of white lake, adopts the solidifying agent of Dyhard RU 100 as phosphorous epoxy resin; The poor heat resistance of sheet material, water-absorbent is big; Adopt the solidifying agent of resol as phosphorous epoxy resin, bonding sheet apparent poor, the fragility of sheet material is big, poor in processability.Second kind of approach, the employing benzoxazine colophony is a matrix resin, adds an amount of phosphorous epoxy resin or phosphorous, nitrogenous solidifying agent; Adding an amount of organic or inorganic filler benzoxazine colophony again has good resistance toheat and low water-intake rate, but fragility is big, the poor processability of sheet material.
Japanese Patent Laid is opened and is disclosed among the clear 61-148619 with combining phosphorus atom to prepare the P contained compound fire retardant on the fatty compounds, is used for the preparation of Halogen copper-clad plate, improved flame retardant resistance, but thermotolerance and wet fastness is bad.In addition, use phosphorus fire-retardant, the various midbodys and the production process of phosphorus flame retardant all have certain toxicity; Phosphorus flame retardant possibly produce toxic gas (like methylphosphine) and toxic substance (like triphenylphosphine etc.) in the incendiary process, its waste possibly cause potential hazard to aquatic environment simultaneously.
Summary of the invention
Therefore the object of the present invention is to provide a kind of halogen and phosphor-free flame-proof epoxy resin composition, not halogen-containing element and phosphoric, and have excellent flame-retardant performance, flame retardant resistance reaches the UL94V-0 level.
Another object of the present invention is to provide the bonding sheet that uses above-mentioned halogen and phosphor-free flame-proof epoxy resin composition to make, have high heat resistance, high reliability, high glass-transition temperature (Tg), flame retardancy, low water absorption, low dielectric loss and low thermal coefficient of expansion.
Another purpose of the present invention is to provide the copper-clad laminate that uses above-mentioned halogen and phosphor-free flame-proof epoxy resin composition to make; Have high heat resistance, high reliability, high glass-transition temperature (Tg), flame retardancy, low water absorption, low dielectric loss, low thermal coefficient of expansion, and have good processing properties.
According to above-mentioned purpose of the present invention, a kind of halogen and phosphor-free flame-proof epoxy resin composition is proposed, by constituent and solvent composition, constituent (by the constituent listed as parts by weight) comprising:
Biphenyl type epoxy resin 50-80 part;
Composite curing agent 20-50 part, composite curing agent is made up of benzoxazine colophony, nitrogenous resol and diaminodiphenylsulfone(DDS);
Filler 10-100 part;
Constituent is dissolved in solvent, and the weight percent that constituent accounts for gross weight is 65%～75%.
Simultaneously, propose a kind of bonding sheet that uses above-mentioned halogen and phosphor-free flame-proof epoxy resin composition to make, be made up of strongthener and the body material that is infiltrated on the strongthener, said body material is said halogen and phosphor-free flame-proof epoxy resin composition.
In addition; A kind of copper-clad laminate that uses above-mentioned halogen and phosphor-free flame-proof epoxy resin composition to make is also proposed; Comprise veneer sheet and be overlaid on the tinsel of the one or both sides of veneer sheet; Veneer sheet comprises the bonding sheet that several pieces fit, and said bonding sheet adopts said halogen and phosphor-free flame-proof epoxy resin composition to process.
Beneficial effect of the present invention: the not halogen-containing and phosphoric of resin combination of the present invention, flame retardant resistance reaches the UL94V-0 level; With its bonding sheet of processing and copper-clad laminate, have high heat resistance, high reliability, high glass-transition temperature (Tg), flame retardancy, low water absorption, low dielectric loss and low thermal coefficient of expansion, and have good processing properties.
Embodiment
Halogen and phosphor-free flame-proof epoxy resin composition of the present invention comprises: constituent and solvent, constituent comprise biphenyl type epoxy resin, benzoxazine colophony, curing catalyst and compounded mix.
The weight proportion of above-mentioned raw materials (by the constituent listed as parts by weight) is:
Biphenyl type epoxy resin 50-80 part;
Composite curing agent 20-50 part;
Curing catalyst 0.01-1.0 part;
Filler 10-100 part;
Solvent is an amount of.
Said biphenyl epoxy resin is the specific epoxy resin that contains biphenyl structural, and its chemical structural formula is:
Biphenyl type epoxy resin, aromatic nucleus occupies bigger ratio in the structure, and the cured article thermotolerance is high, good flame resistance; In resin, owing to contain biphenyl structural, can reduce free volume, improve toughness, reduce water-absorbent.
Said composite curing agent is made up of benzoxazine colophony, nitrogenous resol and diaminodiphenylsulfone(DDS).The benzoxazine resin is one type of nitrogenous ring-opening polymerization resol with heterocycle structures such as phenyl ring and oxazines rings: the existence of phenyl ring and oxazines ring makes this resinoid have outstanding thermotolerance, mechanical property and flame retardant resistance.The benzoxazine colophony that the present invention adopts is the structure that contains many phenyl ring, and its chemical structural formula is:
The nitrogenous resol that adopts has the structure of triazine ring, and its nitrogen content is at 10-30%.The ratio of benzoxazine colophony, nitrogenous resol and diaminodiphenylsulfone(DDS) can be adjusted arbitrarily in the composite curing agent, and its optimum ratio is 5:3:2.
Said curing catalyst is the imidazoles curing catalyst, can adopt in glyoxal ethyline, 1-Methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, the 2-phenyl-4-methylimidazole one or more.
Said filler is mineral filler or/and organic filler, and one or more the mixture in white lake, Marinco H, zeolite, wollastonite, silicon-dioxide, Natural manganese dioxide, Calucium Silicate powder, lime carbonate, clay, talcum and the mica is adopted in mineral filler; Nitrogenous organic filler is adopted in organic filler, is one or more the mixture in trimeric cyanamide, the melamine cyanurate.
Halogen and phosphor-free flame-proof epoxy resin composition of the present invention adopts conventional preparation method to prepare; Solid resin biphenyl epoxy resin and composite curing agent are dissolved in certain solvent; Solvent for use can be one or more in acetone, butanone, pimelinketone, EGME, propylene glycol monomethyl ether, the propylene glycol monomethyl ether vinegar ester etc.; Suitably adjust the solids content 65% to 75% of solution and process glue with solvent; Stirring adds liquid resin and promotor again after dissolving fully, the balance that continues to stir gets final product.
Printed electronic circuit of the present invention is made up of the body material on strongthener and the infiltration strongthener with bonding sheet, and body material is described halogen and phosphor-free flame-proof epoxy resin composition.
The making of bonding sheet of the present invention adopts strongthener to immerse in the glue of above-mentioned halogen and phosphor-free flame-proof epoxy resin composition; The strongthener that impregnation is good dried by the fire 5-8 minute in 170 ℃ baking oven; And behind semicure, process printed electronic circuit and use bonding sheet, said strongthener can adopt natural fiber, organic synthetic fibers, organic fabric and inorganic fibre; For example: adopt glasscloth.
Use in printed circuit board copper-clad laminate of the present invention comprises veneer sheet and is overlaid on the tinsel of the one or both sides of veneer sheet that veneer sheet comprises the said bonding sheet that several pieces are bonding.Said tinsel can also be nickel foil, aluminium foil and SUS paper tinsel etc. except that Copper Foil, and its material is not limit.
The making of use in printed circuit board copper-clad laminate of the present invention is through heating and pressurization, bonding sheet more than two or two is bonded together and process veneer sheet, again will be at the bonding Copper Foil of the one or both sides of veneer sheet; In an embodiment of the present invention, described copper-clad laminate is to use the eight above-mentioned bonding sheets and the Copper Foil of two one ounce (35um is thick) to be superimposed together, and carries out lamination through thermocompressor, thereby is pressed into doublesided copperclad laminate.The lamination of copper-clad laminate need satisfy following requirement: 1, laminated temperature rise rate: the heat-up rate when expecting warm 80-160 degree centigrade should be controlled at 1.0-3.0 degree centigrade/min usually; 2, laminated pressure setting: outer layered material temperature applies full pressure in the time of 80～100 degrees centigrade, and full pressure pressure is about 300psi; When 3, solidifying, control material temperature is at 185 degrees centigrade, and insulation 90min.
Copper-clad laminate (eight bonding sheets) to the above-mentioned use in printed circuit board of processing is surveyed its dielectric dissipation factor, thermotolerance, water-absorbent, CTE, second-order transition temperature, flame retardant resistance and solidified nature, and following embodiment further gives to explain in detail and describe.
Embodiment 1: biphenyl epoxy resin (Japanese chemical drug company produces for marque NC-3000, epoxy equivalent (weight) 280g/eq) 60 weight parts; Benzoxazine colophony (marque XU8282-1, Hensel steps Advanced Materials Corp. and produces) 20 weight parts; Nitrogenous resol (marque PS6313, nitrogen content 20%, hydroxyl equivalent 148, Japanese Gunsaka Chem. Industry Co., Ltd. produces) 12 weight parts; Diaminodiphenylsulfone(DDS) 8 weight parts; Glyoxal ethyline 0.10 weight part; White lake (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts; Silicon-dioxide (median size is 1 to 3 μ m, and purity is more than 99%) 10 weight parts; Marinco H (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts.The solids content of using butanone solvent to regulate glue is 65%, mixes and processes the non-halogen non-phosphate composition epoxy resin.
Embodiment 2: biphenyl epoxy resin (Japanese chemical drug company produces for marque NC-3000, epoxy equivalent (weight) 280g/eq) 70 weight parts; Benzoxazine colophony (marque XU8282-1, Hensel steps Advanced Materials Corp. and produces) 15 weight parts; Nitrogenous resol (marque PS6313, nitrogen content 20%, hydroxyl equivalent 148, Japanese Gunsaka Chem. Industry Co., Ltd. produces) 9 weight parts; Diaminodiphenylsulfone(DDS) 6 weight parts; Glyoxal ethyline 0.15 weight part; White lake (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts; Silicon-dioxide (median size is 1 to 3 μ m, and purity is more than 99%) 10 weight parts; Marinco H (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts.The solids content of using butanone solvent to regulate glue is 65%, mixes and processes the non-halogen non-phosphate composition epoxy resin.
Embodiment 3: biphenyl epoxy resin (Japanese chemical drug company produces for marque NC-3000, epoxy equivalent (weight) 280g/eq) 60 weight parts; Benzoxazine colophony (marque XU8282-1, Hensel steps Advanced Materials Corp. and produces) 20 weight parts; Nitrogenous resol (marque PS6313, nitrogen content 20%, hydroxyl equivalent 148, Japanese Gunsaka Chem. Industry Co., Ltd. produces) 12 weight parts; Diaminodiphenylsulfone(DDS) 8 weight parts; Glyoxal ethyline 0.10 weight part; Melamine cyanurate (median size is 1 to 5 μ m, and purity is more than 95%) 10 weight parts; Silicon-dioxide (median size is 1 to 3 μ m, and purity is more than 99%) 10 weight parts; Marinco H (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts.The solids content of using butanone solvent to regulate glue is 65%, mixes and processes the non-halogen non-phosphate composition epoxy resin.
Comparative example 1: biphenyl epoxy resin (Japanese chemical drug company produces for marque NC-3000, epoxy equivalent (weight) 280g/eq) 60 weight parts; Benzoxazine colophony (marque XU8282-1, Hensel steps Advanced Materials Corp. and produces) 20 weight parts; Nitrogenous resol (marque PS6313, nitrogen content 20%, hydroxyl equivalent 148, Japanese Gunsaka Chem. Industry Co., Ltd. produces) 12 weight parts; Diaminodiphenylsulfone(DDS) 8 weight parts; Glyoxal ethyline 0.10 weight part.The solids content of using butanone solvent to regulate glue is 65%, mixes and processes the non-halogen non-phosphate composition epoxy resin.
Comparative example 2: biphenyl epoxy resin (Japanese chemical drug company produces for marque NC-3000, epoxy equivalent (weight) 280g/eq) 70 weight parts; 25 parts of phenol type resol (solids content 100%) weight parts; Glyoxal ethyline 0.15 weight part; White lake (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts; Silicon-dioxide (median size is 1 to 3 μ m, and purity is more than 99%) 10 weight parts; Marinco H (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts.The solids content of using butanone solvent to regulate glue is 65%, mixes and processes the non-halogen non-phosphate composition epoxy resin.
Comparative example 3: biphenyl epoxy resin (Japanese chemical drug company produces for marque NC-3000, epoxy equivalent (weight) 280g/eq) 70 weight parts; Nitrogenous resol (marque PS6313, nitrogen content 20%, hydroxyl equivalent 148, Japanese Gunsaka Chem. Industry Co., Ltd. produces) 20 weight parts; Glyoxal ethyline 0.10 weight part; White lake (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts; Silicon-dioxide (median size is 1 to 3 μ m, and purity is more than 99%) 10 weight parts; Marinco H (median size is 1 to 5 μ m, and purity is more than 99%) 10 weight parts.The solids content of using butanone solvent to regulate glue is 65%, mixes and processes the non-halogen non-phosphate composition epoxy resin.
Table 1 is depicted as the prescription comparison diagram of compsn in the foregoing description and the comparative example:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Biphenyl epoxy resin | 60 | 70 | 60 | 60 | 70 | 70 |
| Benzoxazine colophony | 20 | 15 | 20 | 20 | - | - |
| Nitrogenous resol | 12 | 9 | 12 | 12 | - | 20 |
| Diaminodiphenylsulfone(DDS) | 8 | 6 | 8 | 8 | - | - |
| Phenol type resol | - | - | - | - | 25 | - |
| Glyoxal ethyline | 0.10 | 0.15 | 0.10 | 0.10 | 0.15 | 0.10 |
| White lake | 10 | 10 | - | - | 10 | 10 |
| Melamine cyanurate | - | - | 10 | - | - | - |
| Silicon-dioxide | 10 | 10 | 10 | - | 10 | 10 |
| Marinco H | 10 | 10 | 10 | - | 10 | 10 |
| Butanone | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
| Solids content (%) | 65 | 65 | 65 | 65 | 65 | 65 |
Table 2
Table 2 is depicted as the parameter value that the copper-clad laminate processed to the compsn that adopts the foregoing description and comparative example is tested, and testing method is following:
1) second-order transition temperature (Tg):, measure according to the DSC method of IPC-TM-6502.4.25 defined according to dsc (DSC).
2) stripping strength (PS) is tested the stripping strength of metal cap rock according to " after the thermal stresses " experiment condition in the IPC-TM-6502.4.8 method.
3) incendivity: measure according to UL94 vertical combustion method.
4) thermally stratified layer time T-300: measure according to the IPC-TM-6502.4.24.1 method.
5) thermal expansivity Z axle CTE (TMA): measure according to the IPC-TM-6502.4.24. method.
6) heat decomposition temperature Td: measure according to the IPC-TM-6502.4.26 method.
7) water-absorbent: measure according to the IPC-TM-6502.6.2.1 method.
8) dielectric loss angle tangent:, measure the dielectric loss angle tangent under the 1MHz according to IPC-TM-6502.5.5.9 according to the resonant method of using stripline runs.
9) punching property: the base material that 1.60mm is thick is put on the punch die of certain figure and carries out punching, and Kong Bianwu encloses in vain with visual inspection (h1), (h2) Kong Bianyou Bai Quan, (h3) split in the limit, hole, in the table respectively with symbol zero, △, * expression.
10) content of halogen test: measure according to the IPC-TM-6502.3.41 method.
In sum, the not halogen-containing and phosphoric of resin combination of the present invention, flame retardant resistance reaches the UL94V-0 level; With its bonding sheet of processing and copper-clad laminate, have high heat resistance, high reliability, high glass-transition temperature (Tg), flame retardancy, low water absorption, low dielectric loss and low thermal coefficient of expansion, and have good processing properties.
Above embodiment; Be not that the content of compsn of the present invention is done any restriction; Every foundation technical spirit of the present invention or compsn composition or content all still belong in the scope of technical scheme of the present invention any trickle modification, equivalent variations and modification that above embodiment did.
Claims (8)
1. a halogen and phosphor-free flame-proof epoxy resin composition is characterized in that, by constituent and solvent composition, constituent comprises by the constituent listed as parts by weight:
Biphenyl type epoxy resin 50-80 part;
Composite curing agent 20-50 part, composite curing agent is made up of benzoxazine colophony, nitrogenous resol and diaminodiphenylsulfone(DDS);
Filler 10-100 part;
Constituent is dissolved in solvent, and the weight percent that constituent accounts for gross weight is 65%～75%;
Said biphenyl epoxy resin is the epoxy resin that contains biphenyl structural, and its chemical structural formula is:
2. halogen and phosphor-free flame-proof epoxy resin composition as claimed in claim 1 is characterized in that, said constituent also comprises: curing catalyst 0.01-1.0 part.
3. halogen and phosphor-free flame-proof epoxy resin composition as claimed in claim 1 is characterized in that, said nitrogenous resol has triazine ring structure, and its nitrogen content is 10-30%.
4. halogen and phosphor-free flame-proof epoxy resin composition as claimed in claim 1 is characterized in that, the ratio of said benzoxazine colophony, nitrogenous resol and diaminodiphenylsulfone(DDS) is 5: 3: 2.
5. halogen and phosphor-free flame-proof epoxy resin composition as claimed in claim 1; It is characterized in that; Said filler is mineral filler or/and organic filler, and one or more the mixture in white lake, Marinco H, zeolite, wollastonite, silicon-dioxide, Natural manganese dioxide, Calucium Silicate powder, lime carbonate, clay, talcum and the mica is adopted in mineral filler; Nitrogenous organic filler is adopted in organic filler, is one or more the mixture in trimeric cyanamide, the melamine cyanurate.
6. halogen and phosphor-free flame-proof epoxy resin composition as claimed in claim 2; It is characterized in that; Said curing catalyst is the imidazoles curing catalyst, the mixture of one or more in employing glyoxal ethyline, 1-Methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, the 2-phenyl-4-methylimidazole.
7. bonding sheet that uses halogen and phosphor-free flame-proof epoxy resin composition as claimed in claim 1 to make; Form by strongthener and the body material that is infiltrated on the strongthener; It is characterized in that said body material is said halogen and phosphor-free flame-proof epoxy resin composition.
8. copper-clad laminate that uses halogen and phosphor-free flame-proof epoxy resin composition as claimed in claim 1 to make; Comprise veneer sheet and be overlaid on the tinsel of the one or both sides of veneer sheet; Veneer sheet comprises the bonding sheet that several pieces fit; It is characterized in that said bonding sheet adopts said halogen and phosphor-free flame-proof epoxy resin composition to process.
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