CN1548473A - Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process - Google Patents
Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process Download PDFInfo
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- CN1548473A CN1548473A CNA031265189A CN03126518A CN1548473A CN 1548473 A CN1548473 A CN 1548473A CN A031265189 A CNA031265189 A CN A031265189A CN 03126518 A CN03126518 A CN 03126518A CN 1548473 A CN1548473 A CN 1548473A
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Abstract
The no-halide fire-retardant glue liquid consists of benzoxazine resin, fire-retardant epoxy resin, curing agent, curing promoter, solvent and fire retardant. The no-halide fire-retardant copper-clad board with the no-halide fire-retardant glue is produced through the following steps: preparing the no-halide fire-retardant glue liquid, soaking cloth with the no-halide fire-retardant glue liquid, extruding the soaked cloth in a vertical or horizontal extruder to produce semi-cured sheet, combining the cut semi-cured sheet with copper foil in a vacuum hot press at certain temperature, pressure, vacuum degree and other conditions to obtain the copper-clad board. The no-halide fire-retardant glue liquid and the no-halide fire-retardant copper-clad board of the present invention are environment friendly.
Description
Technical field
The present invention relates to a kind of glue, refer more particularly to a kind of glue of halogen-free flameproof copper clad foil substrate, the invention still further relates to a kind of halogen-free flameproof copper clad foil substrate that uses this glue and preparation method thereof.
Background technology
The halogen-free flameproof copper clad foil substrate is in processing, application, fire, waste treatment, comprise recovery, bury, in the burning process, can not produce human body and the deleterious material of environment, specifically, it is batch not flame retardant type copper-clad plate of element such as Halogen, antimony, this copper-clad plate has the amount of being fuming when burning few, the characteristics that bad smell is little.
Wish Datong District's " non-halogen FR-4 copper-clad plate development progress ", " insulating material ", 2002, (4), P30-36, discussed non-halogen FR-4 copper-clad plate from the state of the art development, in Japan, developing into second level stage at present: the fs: the non-halogen FR-4 product of year developing in 90 year mid-term to 1998 of Japanese copper clad foil substrate (CCL) producer. this class CCL can reach the general standard performance demands, it is the non-halogen Resins, epoxy compositional system of main flame retardant that its resin is formed employing phosphorus, can reach the general characteristic requirement, comprise that flame retardant resistance reaches the UL94-V0 level.The grasp of this stage phosphorus compound and Resins, epoxy synthesis technology is also not really deep, and a part of producer simply also adopts the addition type method to go to reach flame retardant resistance, causes some performance such as wet fastness on the low side.Subordinate phase, 1999 are so far, and the cutting edge technology of Japanese non-halogen FR-4 develops into this stage, and it is the non-halogen Resins, epoxy compositional system of main flame retardant that this stage is adopted phosphorus, and characteristic reaches whole equalization request---high Tg, high working property, low cost etc.
Benzoxazine is the benzo hexa-member heterocycle system that a class is made of Sauerstoffatom and nitrogen-atoms, characteristics with ring-opening polymerization, not having small molecules during polymerization discharges, form the reticulated structure of similar resol after the polymerization, the cure shrinkage of goods is little, and porosity is low, excellent mechanical property, electric property and flame retardant properties are arranged.Chinese patent ZL94111852.5 discloses benzoxazine resin synthetic technology route, the benzoxazine resin composite materials has good preparation and forming process, physical and mechanical properties is good, is suitable for high-temperature-resistant structure material and the electrically insulating material of making 150～180 ℃ of life-time service.
Summary of the invention
The object of the invention provides the glue of the copper clad foil substrate that satisfies environmental protection requirement; it is the glue of halogen-free flameproof copper-clad plate substrate; another object of the present invention provides the halogen-free flameproof copper-clad plate substrate of environmental protection, and also purpose of the present invention provides the preparation method of halogen-free flameproof copper-clad plate substrate.
The present invention seeks to realize like this: halogen-free flameproof substrate glue, it is formed and content is:
Benzoxazine resin 30-80 part (in the resin solid weight part);
Fire retarding epoxide resin 20-70 part (in the resin solid weight part);
The 1-5% of curing agent resin total solid weight;
The 0.01-0.5% of curing catalyst resin total solid weight;
The 50-80% of solvent resin total solid weight;
The 5-40% of fire retardant resin total solid weight.
Described halogen-free flameproof glue, wherein the benzoxazine resin is the technological line synthetic that provides according to Chinese patent ZL94111852.5, structural formula is:
Described fire retarding epoxide resin is a phosphorous epoxy resin, or the mixture of phosphorous epoxy resin and halogen-free epoxy resin;
Wherein phosphorous epoxy resin is:
Or
Halogen-free epoxy resin is:
(1) bisphenol A diglycidyl ether
N=1～10 wherein
(2) Bisphenol F diglycidylether
N=1～10 wherein
(3) bisphenol-S diglycidyl ether
N=1～10 wherein
(4) the linear cresoform polyglycidyl ether of linear phenolic aldehyde polyglycidyl ether (5)
N=1～5 wherein
Or (6) glycidyl amine type epoxy resin
Described fire retardant is a kind of mixture in following organic phosphonium flame retardant or the inorganic combustion inhibitor.
(1) organic phosphonium flame retardant
Or
(2) inorganic combustion inhibitor
Red phosphorus, Dawsonite Kompensan, magnesium hydroxide, zinc borate, silicon-dioxide or aluminium hydroxide.
Described halogen-free flameproof glue, wherein the solidifying agent general formula is:
H
2N-R-NH
2
Wherein R is:
C
nH
2n(n≥2)，
Or
In a kind of.
Described halogen-free flameproof glue, wherein curing catalyst is: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethyl imidazol(e) or 2-phenylimidazole are wherein any.
Described halogen-free flameproof glue, wherein solvent is: toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, Propylene Glycol Dimethyl Ether, 1-Methoxy-2-propyl acetate, methylethylketone, pimelinketone or acetone.
In the present invention, ring-opening polymerization takes place in the benzoxazine resin under the condition that solidifying agent exists, generate polyphenyl and oxazines resin.Reaction formula is as follows:
The open loop self-polymeric reaction of benzoxazine is as follows:
Polyphenyl that generates after the benzoxazine open loop and oxazines are a kind of reticulated structures of similar resol, can be used as curing agent for epoxy resin and further react.
Halogen-free flameproof copper-clad plate substrate of the present invention, its coating contains the glue of above-mentioned prescription.
The forming technology of halogen-free flameproof copper-clad plate substrate of the present invention comprises the steps,
1. the preparation of halogen-free flameproof substrate glue
The preparation of halogen-free flameproof substrate glue
Under the room temperature, in proportion container, add the solution that is dissolved with solidifying agent and is dissolved with organic phosphonium flame retardant respectively, stir down, add phosphorous epoxy resin solution, benzoxazine resin respectively and be dissolved with the solution of curing catalyst, continue to stir after 30 minutes, add inorganic combustion inhibitor, restir 6 hours, the gel time of sampling and testing glue (170 ℃ of hot plates), its gel time is between 200～300 seconds.
Should note in the present invention:
A. the adding mode of solidifying agent and curing catalyst:
Before use, should earlier solidifying agent and curing catalyst be dissolved in solvent, be mixed with solution, stand-by.
B. solvent
With dimethyl formamide DMF, pimelinketone, butanone etc. or its combination as solvent system, with acetone as thinner.
C. gelation time is regulated
The gelation time of the glue of preparing can be regulated with the add-on of curing catalyst.
Gelation time: the gelation time of resin all can prepare sheet material by adhesive applicator and press in 200～300 seconds scope behind the glue through joining.
Solid content: the solid content of general glue is at 50%--70%wt.
Storage period: the glue of being prepared can at room temperature be stored more than the two weeks.
2. impregnation
The adhesive plaster that will soak halogen-free flameproof substrate glue by control wind-warm syndrome and furnace temperature, makes prepreg by vertical or horizontal type impregnation machine.
3. compacting
Prepreg is cut into certain size, and it puts into the vacuum hotpressing machine after making up with Copper Foil up and down, presses down at certain temperature, pressure, time and vacuum condition and makes copper clad foil substrate.
Beneficial effect of the present invention: glue of the present invention has adopted the starting material of halogen-free flameproof, and glue and copper-clad plate substrate are being produced and used and can both satisfy environmental protection requirement.
Embodiment:
1, specific embodiment prescription (following " part " is weight part):
60 parts of one of embodiment benzoxazine resins, 20 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (3)), phosphorous epoxy resin is (in the phosphorous epoxy resin structural formula (7), n=1～10) 20 parts, 3.5 parts of benzidines, 0.03 part of 2-ethyl-4-methylimidazole, 65 parts of methylethylketones, 5 parts of organic phosphonium flame retardants (b in organic phosphonium flame retardant structural formula), 15 parts of inorganic combustion inhibitor zinc borates.
65 parts of the dibenzo oxazines resins of embodiment, phosphorous epoxy resin is (in the phosphorous epoxy resin structural formula (7), n=1～10) 35 parts, N, N '-4,3.5 parts of 4 '-diphenylmethane diamines, 0.06 part of 2-ethyl-4-methylimidazole, 65 parts of dimethyl formamides, 3.5 parts of organic phosphonium flame retardants (h in organic phosphonium flame retardant structural formula), 10.5 parts of inorganic combustion inhibitor magnesium hydroxides.
50 parts of the three benzo oxazines resins of embodiment, 25 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (6), n=1～10), phosphorous epoxy resin is (in the phosphorous epoxy resin structural formula (7), n=1～10) 25 parts, N, N '-4,2.5 parts of 4 '-diphenylmethane diamines, 0.05 part of glyoxal ethyline, 35 parts of dimethyl formamides, 20 parts of methylethylketones, 3 parts of organic phosphonium flame retardants (d in organic phosphonium flame retardant structural formula), 22 parts in inorganic combustion inhibitor aluminium hydroxide.
60 parts of the four benzoxazine resins of embodiment, 25 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (7), n=1～10), halogen-free epoxy resin is (in the halogen-free epoxy resin structural formula (5), n=1～6) 15 parts, N, N '-4,4 parts of 4 '-two lauseto neu diamines, 0.02 part of 2-ethyl-4-methylimidazole, 35 parts of dimethyl formamides, 30 parts of Propylene Glycol Dimethyl Ether, 2.5 parts of organic phosphonium flame retardants (d in organic phosphonium flame retardant structural formula), 30 parts in aluminium hydroxide.
50 parts of the pentaphene of embodiment and oxazines resins, 40 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (8), n=1～10), halogen-free epoxy resin is (in the halogen-free epoxy resin structural formula (1), n=1～10) 10 parts, N, N '-4,4 parts of 4 '-phenyl ether diamines, 0.02 part of glyoxal ethyline, 70 parts of dimethyl formamides, 2 parts of organic phosphonium flame retardants (f in organic phosphonium flame retardant structural formula), 23 parts in inorganic combustion inhibitor aluminium hydroxide.
65 parts of the six benzoxazine resins of embodiment, 25 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (1)), 10 parts of halogen-free epoxy resins (in the halogen-free epoxy resin structural formula (4), n=1～10), N, N '-4,4 parts of 4 '-diphenylmethane diamines, 0.03 part of 2-ethyl-4-methylimidazole, 30 parts of pimelinketone, 30 parts of Propylene Glycol Dimethyl Ether, and organic phosphonium flame retardant (in organic phosphonium flame retardant structural formula a) 2 parts, 20 parts of inorganic combustion inhibitor magnesium hydroxides.
60 parts of the seven benzoxazine resins of embodiment, 25 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (1)), 15 parts of halogen-free epoxy resins (in the halogen-free epoxy resin structural formula (6)), N, N '-4,5 parts of 4 '-diphenylmethane diamines, 0.04 part of 2-phenylimidazole, 35 parts of dimethyl formamides, 30 parts of pimelinketone, 1 part of organic phosphonium flame retardant (e in organic phosphonium flame retardant structural formula), 35 parts in inorganic combustion inhibitor aluminium hydroxide.
40 parts of the eight benzoxazine resins of embodiment, 30 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (1)), 30 parts of halogen-free epoxy resins (in the halogen-free epoxy resin structural formula (5), n=1～5), N, N '-4,5 parts of 4 '-phenyl ether diamines, 0.35 part of 2-phenylimidazole, 40 parts of pimelinketone, 30 parts of Propylene Glycol Dimethyl Ether, 5 parts of organic phosphonium flame retardants (f in organic phosphonium flame retardant structural formula), 25 parts in aluminium hydroxide.
70 parts of the nine benzoxazine resins of embodiment, phosphorous epoxy resin is (in the phosphorous epoxy resin structural formula (8), n=1～10) 30 parts, N, N '-4,4 parts of 4 '-phenyl ether diamines, 0.03 part of 2-ethyl-4-methylimidazole, 35 parts of dimethyl formamides, 30 parts of Propylene Glycol Dimethyl Ether, organic phosphonium flame retardant (g in organic phosphonium flame retardant structural formula, R=CH
3, C
2H
5, n=1-2) 1.5 parts, 35 parts of inorganic combustion inhibitor Aluminum Carbonate Basics.
40 parts of the ten benzoxazine resins of embodiment, phosphorous epoxy resin is (in the phosphorous epoxy resin structural formula (7), n=1～10) 40 parts, 20 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (7), n=1～10), 4 parts of mphenylenediamines, 0.04 part of glyoxal ethyline, 35 parts of dimethyl formamides, 30 parts of pimelinketone, 4 parts of organic phosphonium flame retardants (b in organic phosphonium flame retardant structural formula), 3 parts in inorganic combustion inhibitor aluminium hydroxide.
50 parts of the 11 benzoxazine resins of embodiment, 25 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (4)), 25 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (8), n=1～10), N, N '-4,2.5 parts of 4 '-two lauseto neu diamines, 0.08 part of 2-phenylimidazole, 35 parts of dimethyl formamides, 30 parts of methylethylketones, 1.8 parts of organic phosphonium flame retardants (c in organic phosphonium flame retardant structural formula), 30 parts of inorganic combustion inhibitor silicon-dioxide.
35 parts of the ten dibenzo oxazines resins of embodiment, and phosphorous epoxy resin (in the phosphorous epoxy resin structural formula (2), R=H, CH
3Or C
2H
5) 40 parts, halogen-free epoxy resin is (in the halogen-free epoxy resin structural formula (5), n=1～5) 25 parts, N, N '-4,3.5 parts of 4 '-diphenylmethane diamines, 0.04 part of 2-ethyl imidazol(e), 35 parts of dimethyl formamides, 30 parts of 1-Methoxy-2-propyl acetates, 5 parts of organic phosphonium flame retardants (h in organic phosphonium flame retardant structural formula), 30 parts in inorganic combustion inhibitor aluminium hydroxide.
55 parts of the 13 benzo oxazines resins of embodiment, phosphorous epoxy resin is (in the phosphorous epoxy resin structural formula (5), n=1～10) 30 parts, 15 parts of phosphorous epoxy resins (in the structural formula (3)), 2.5 parts of benzidines, 0.06 part of glyoxal ethyline, 30 parts of N,N-DIMETHYLACETAMIDEs, 30 parts of pimelinketone, 1.5 parts of organic phosphonium flame retardants (b in organic phosphonium flame retardant structural formula), 30 parts of inorganic combustion inhibitor zinc borates.
65 parts of the 14 benzoxazine resins of embodiment, 25 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (5)), 10 parts of halogen-free epoxy resins (in the halogen-free epoxy resin structural formula (4), n=1～10), N, N '-4,3.5 parts of 4 '-phenyl ether diamines, 0.09 part of 2-phenylimidazole, 40 parts of dimethyl formamides, 20 parts of Propylene Glycol Dimethyl Ether, 3 parts of organic phosphonium flame retardants (c in organic phosphonium flame retardant structural formula), 35 parts in inorganic combustion inhibitor aluminium hydroxide.
45 parts of ten pentaphenes of embodiment and oxazines resins, phosphorous epoxy resin is (in the phosphorous epoxy resin structural formula (7), n=1～10) 25 parts, 10 parts of phosphorous epoxy resins (in the phosphorous epoxy resin structural formula (1)), halogen-free epoxy resin is (in the halogen-free epoxy resin structural formula (5), n=1～5) 20 parts, N, N '-4,3.5 parts of 4 '-diphenylmethane diamines, 0.03 part of glyoxal ethyline, 25 parts of dimethyl formamides, 35 parts of methylethylketones, and organic phosphonium flame retardant (in organic phosphonium flame retardant structural formula a) 5 parts, 30 parts of inorganic combustion inhibitor magnesium hydroxides.
2. the preparation technology of glue
1) solution and the curing agent solution with organic phosphonium flame retardant adds in the proportion container respectively;
2) stir the solution (curing catalyst/solvent=1: 6 (ratio of weight and number)) that adds phosphorous epoxy resin (or containing halogen-free epoxy resin), benzoxazine resin and curing catalyst down respectively;
3) behind the stirring 30min, add inorganic combustion inhibitor;
4) continue to stir 6 hours, the gel time of sampling and testing glue (170 ℃ of constant temperature hot plates) is (200～300) second.
3. impregnation
The adhesive plaster that will soak the halogen-free flameproof glue by conditions such as control extruding wheel speed, linear speed, wind-warm syndrome and furnace temperature, makes prepreg by vertical or horizontal type impregnation machine.
With vertical impregnation machine is example:
The proportion of Varnish: 1.10～1.20;
Extruding wheel speed :-1.8～-2.5 ± 0.1M/min;
Main line speed: 5～14M/min;
Wind-warm syndrome: 130～160 ℃;
Furnace temperature: 140～180 ℃.
Make prepreg by above condition.
4. compacting
After the prepreg that cuts and Copper Foil combined, put into the vacuum hotpressing machine, obtaining substrate by following formula compacting.
Temperature formula: 130 ℃/30min+160 ℃/30min+180 ℃/20min+
210℃/180min
Pressure formula: 20Kgf.cm
-2/ 30min+50Kgf.cm
-2/ 15min+
95Kgf.cm
-2/150min+20Kgf.cm
-2/65min
Vacuum is set: 30mmHg/130min+760mmHg/130min
5. following is the substrate performance of part prescription:
| Test event | Testing apparatus | Test condition | Two of embodiment | Three of embodiment | Five of embodiment | Seven of embodiment | Ten of embodiment | |
| Strengthen thermotolerance, Sec. | 288 ℃ of tin stoves of pressure kettle | ??PCT2h ??288℃Dipping | ????120 | ????180 | ????160 | ????200 | ????100 | |
| Water-intake rate, % | Beaker | ??D-24/23 | ????0.142 | ????0.153 | ????0.201 | ????0.168 | ????0.284 | |
| α 1，ppm/℃ | The TA-2940TMA thermal analyzer | ? ? ??50-195℃， ??10℃/min | ????47.3 | ????43.2 | ????45.3 | ????42.9 | ????35.7 | |
| α 2，ppm/℃ | ????278 | ????264 | ????277 | ????204 | ????213 | |||
| Tg，℃ | ????160.7 | ????165.6 | ????160.07 | ????164.54 | ????168.6 | |||
| T300 | ??50-300℃， ??10℃/min， ??ISO30min | ????＞30in | ????＞30in | ????＞30in | ????＞30in | ????＞30in | ||
| Tg 1，℃ | The TA-2940DSC thermal analyzer | ??50-190℃， ??20℃/min， ??ISO15min | ????158.4 | ????170.06 | ????166.63 | ????167.17 | ????168.6 | |
| Tg 2，℃ | ??50-195℃， ??20℃/min， | ????160.12 | ????170.81 | ????168.74 | ????169.66 | ????171.1 | ||
| ΔTg，℃ | ??--- | ????1.72 | ????0.85 | ????2.11 | ????2.49 | ????2.5 | ||
| Flexural strength, N/mm 2 | Radially | Omnipotent puller system | ??IPC-TM-650 ??2.4.4 | ????534.6 | ????541.4 | ????505.7 | ????727.3 | ????550.8 |
| Broadwise | ????475.8 | ????485.3 | ????460.1 | ????516.7 | ????470.3 | |||
| Flame retardant resistance 94V-0 | The Bunsen burner iron stand | ??UL94V-0 | ????Pass | ????Pass | ????Pass | ????Pass | ????Pass | |
Claims (10)
1. halogen-free flameproof glue, component and content thereof:
Benzoxazine resin 30-80 part (in the resin solid weight part);
Fire retarding epoxide resin 20-70 part (in the resin solid weight part);
The 1-5% of curing agent resin total solid weight;
The 0.01-0.5% of curing catalyst resin total solid weight;
The 50-80% of solvent resin total solid weight;
The 5-40% of fire retardant resin total solid weight.
2. halogen-free flameproof glue according to claim 1, wherein the structural formula of benzoxazine resin is:
3. halogen-free flameproof glue according to claim 1, wherein fire retarding epoxide resin is a phosphorous epoxy resin, or the mixture of phosphorous epoxy resin and halogen-free epoxy resin.
4. halogen-free flameproof glue according to claim 3, wherein phosphorous epoxy resin is:
Or
In any;
Described halogen-free epoxy resin is:
(1) bisphenol A diglycidyl ether
n＝1～10
(2) Bisphenol F diglycidylether
n＝1～10
(3) bisphenol-S diglycidyl ether
n＝1～10
(4) the linear cresoform polyglycidyl ether of linear phenolic aldehyde polyglycidyl ether (5)
n＝1～5??????????????????????????????????????????????n＝1～5
Or (6) glycidyl amine type epoxy resin
In any.
5. halogen-free flameproof glue according to claim 1 is characterized in that: described fire retardant is one or both a mixture in a kind of and (2) inorganic combustion inhibitor in following (1) organic phosphonium flame retardant:
(1) organic phosphonium flame retardant
Or
(2) inorganic combustion inhibitor
Red phosphorus, Dawsonite Kompensan, magnesium hydroxide, zinc borate, silicon-dioxide or aluminium hydroxide.
6. halogen-free flameproof glue according to claim 1, wherein solidifying agent is:
H
2N-R-NH
2
Wherein R is:
C
nH
2n(n≥2)，
In a kind of.
7. halogen-free flameproof glue according to claim 1, wherein curing catalyst is: glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-ethyl imidazol(e) or 2-phenylimidazole are wherein any.
8. halogen-free flameproof glue according to claim 1, wherein solvent is: toluene, dimethyl formamide, N,N-DIMETHYLACETAMIDE, Propylene Glycol Dimethyl Ether, 1-Methoxy-2-propyl acetate, methylethylketone, pimelinketone or acetone.
9. halogen-free flameproof copper-clad plate substrate, its coating contain among the claim 1-8 each glue.
10. the preparation method of the described halogen-free flameproof copper-clad plate of claim 9, this method may further comprise the steps:
A. the preparation of halogen-free flameproof glue
Under the room temperature, in proportion container, add the solution that is dissolved with solidifying agent and is dissolved with organic phosphonium flame retardant respectively, stir down, add fire retarding epoxide resin solution, benzoxazine resin respectively and be dissolved with the solution of curing catalyst, continue to stir after 30 minutes, add inorganic combustion inhibitor, restir 6 hours, the gel time of sampling and testing glue (170 ℃ of hot plates), its gel time is between 200～300 seconds;
B. impregnation
The adhesive plaster that will soak the halogen-free flameproof glue by conditions such as control extruding wheel speed, linear speed, wind-warm syndrome and furnace temperature, makes prepreg by vertical or horizontal type impregnation machine;
C. compacting
After the prepreg that cuts and Copper Foil combined, put into the vacuum hotpressing machine, press down in conditions such as certain temperature, pressure, time and vacuum and make substrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031265189A CN1296433C (en) | 2003-05-09 | 2003-05-09 | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031265189A CN1296433C (en) | 2003-05-09 | 2003-05-09 | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process |
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| CN1296433C CN1296433C (en) | 2007-01-24 |
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| US5443911A (en) * | 1990-05-21 | 1995-08-22 | Gurit-Essex Ag | Curable resins comprising halogenated epoxy resins and 1-oxa-3-aza tetraline compounds, method for preparing and use of resins |
| CN1058738C (en) * | 1994-07-29 | 2000-11-22 | 四川联合大学 | Open-loop polymerized phenolic resin and relevant composite fibre-reinforced material |
| JP2001271070A (en) * | 2000-03-27 | 2001-10-02 | Asahi Kasei Corp | Flame retardant |
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| JP4951816B2 (en) * | 2001-03-30 | 2012-06-13 | 日立化成工業株式会社 | Insulating resin composition for printed wiring board and use thereof |
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