CN1055434C - Single side copper-clad laminate - Google Patents
Single side copper-clad laminate Download PDFInfo
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- CN1055434C CN1055434C CN95115767A CN95115767A CN1055434C CN 1055434 C CN1055434 C CN 1055434C CN 95115767 A CN95115767 A CN 95115767A CN 95115767 A CN95115767 A CN 95115767A CN 1055434 C CN1055434 C CN 1055434C
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- melmac
- paper base
- base material
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- 239000000463 material Substances 0.000 claims abstract description 94
- 229920005989 resin Polymers 0.000 claims abstract description 74
- 239000011347 resin Substances 0.000 claims abstract description 74
- 150000002989 phenols Chemical class 0.000 claims abstract description 52
- 239000005011 phenolic resin Substances 0.000 claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 38
- 239000011889 copper foil Substances 0.000 claims abstract description 36
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 49
- 229920001568 phenolic resin Polymers 0.000 claims description 38
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 abstract description 15
- 239000004640 Melamine resin Substances 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 description 50
- 230000001070 adhesive effect Effects 0.000 description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 38
- 239000004922 lacquer Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000012545 processing Methods 0.000 description 18
- 238000004080 punching Methods 0.000 description 18
- 239000002383 tung oil Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000007598 dipping method Methods 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 13
- 230000005012 migration Effects 0.000 description 13
- 238000013508 migration Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- -1 melmac Polymers 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 2
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 2
- 240000002834 Paulownia tomentosa Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- MJYQFWSXKFLTAY-OVEQLNGDSA-N (2r,3r)-2,3-bis[(4-hydroxy-3-methoxyphenyl)methyl]butane-1,4-diol;(2r,3r,4s,5s,6r)-6-(hydroxymethyl)oxane-2,3,4,5-tetrol Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O.C1=C(O)C(OC)=CC(C[C@@H](CO)[C@H](CO)CC=2C=C(OC)C(O)=CC=2)=C1 MJYQFWSXKFLTAY-OVEQLNGDSA-N 0.000 description 1
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000004426 flaxseed Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
The present invention provides a predetermined number of paper base material prepregs each obtained by successively infiltrating a melamine resin modified phenol resin and a thermosetting resin into a paper base material and drying the impregnated base are superposed one upon another and copper foil is superposed on the single surface of the superposed one to be pressed under heating to obtain a single-sided copper clad laminated sheet. In this laminated sheet, the adhesion amt. of the melamine resin modified phenol resin is set to 21-25wt.% with respect to the outermost paper base material on the side opposite to the copper foil and 15-20wt.% with respect to the other paper base materials.
Description
The present invention relates to single side copper-clad laminate.
Single side printed wiring board processes on the enterprising line of single side copper-clad laminate road.
Single side copper-clad laminate be with paper base material heat of immersion thermosetting resin lacquer and drying and preforming material, the number of getting regulation overlaps, and a side last Copper Foil that changes therein, the heating pressurization is made and is formed.
Paper base material can be used lint paper, brown paper etc., so paper base material direct impregnation thermosetting resin lacquer, then the compatibility of paper base material and thermosetting resin is poor, thereby adopt the paper base material dipping, and heat of immersion thermosetting resin, Gan Zao method then after drying with the melmac resin modified phenol resin.In existing this method, the dipping adhesive capacity with the melmac resin modified phenol resin forms branch admittedly by resin, is paper base material and 15-20 weight % with the total amount of the resin modified phenolic resins of melamine.The so-called primary coat of the operation of impregnated melamine resin resin modified phenol resin, and with behind the melmac resin modified phenol resin impregnation drying again the operation of heat of immersion thermosetting resin be called face and be coated with.
Can use phenolic resins, melmac, unsaturated polyester resin etc. as the face thermosetting resin that uses of resinizing.Particularly, in order to obtain the good laminate of punching processing, should use dry oil modified phenolic resin.Make phenolic resin modified drying oil can use tung oil, dehydrated castor oil, flaxseed wet goods, phenols can use phenol, metacresol, paracresol, orthoresol, isopropyl-phenol, p-t-butyl phenol, to isopropenyl phenol paper polymers, nonyl phenol, bisphenol-A etc.Copper Foil in order to improve the bonding strength with substrate, can use the Copper Foil that is adhering to adhesive.
Recently, beginning forms through hole through punching processing on single side printed wiring board, is connected with the silver paste circuit that the back side forms with this kind through hole between the circuit on surface (Copper Foil side).
As circuit between add voltage, silver is that ionization and be moved (this phenomenon be called silver migration) become the reason of defective insulation, and cause short circuit accident.
The amount of resin of primary coat is as increasing, and then the performance of tolerance silver migration improves, but the punching processing variation.
The objective of the invention is the paper base material dipping with the melmac resin modified phenol resin, and after drying, the heat of immersion thermosetting resin, dry then, obtain the paper base material preforming material and get the overlapping of regulation number, Copper Foil on the one side changes is not sacrificed the punching processing performance again, and anti-silver-colored migration performance is also improved in the process that obtains single side copper-clad laminate is pressurizeed in heating.
Feature of the present invention is: paper base material floods with the melmac resin modified phenol resin, and after drying, the heat of immersion thermosetting resin, dry then, obtain the paper base material preforming material, getting the regulation number overlaps, Copper Foil on the one side changes, again when the heating pressurization obtains single side copper-clad laminate, for each paper base material, with the adhered resin amount of melmac resin modified phenol resin, to the outermost paper base material opposite, for paper base material with the 21-25 weight % of the total amount of melmac resin modified phenol resin with Copper Foil, be preferably 21-23 weight %, to other paper base materials,, be preferably 17-19 weight % for paper base material with the 15-20 weight % of the total amount of melmac resin modified phenol resin.
Used paper base material is brown paper, lint paper etc. among the present invention, the heavy 115-140g/m of the most handy paper
2Paper base material.
Used among the present invention can be the product of melmac and phenol and the reaction of formaldehyde cocondensation, the perhaps mixture of melmac and phenolic resins with cyanurotriamide modified phenolic resins.Cyanurotriamide modified amount, is preferably 18-25 weight %, yet is not limited to this value about available melamine 20 weight % for the solid formation branch with the melmac resin modified phenol resin.
By melamine and phenol and the preparation of formaldehyde cocondensation occasion with the resin modified phenolic resins of melamine, for example can be in the presence of base catalyst, melamine and formaldehyde are reacted 90-150 minute (was good with 100-140 minute) down 60-80 ℃ (is good with 65-75 ℃), in reaction mixture, add phenols then, formaldehyde and base catalyst react 20-45 minute (was good with 25-40 minute) down 70-100 ℃ (is good with 80-95 ℃) and make.This reaction can fully be carried out under normal pressure usually.
As formaldehyde source, available formalin, paraformaldehyde etc.The consumption of common formaldehyde is a 0.5-0.8 times of weight of melamine weight when reacting with melamine, be preferably 0.55-0.75 times of weight, the amount of the formaldehyde that adds simultaneously with phenols is generally 0.25-0.45 times of weight of phenols weight, is preferably 0.3-0.4 times of weight.
As above-mentioned base catalyst, available such as ammonia, hexa, trimethylamine etc.The consumption of base catalyst is generally the 0.5-3 weight % of melamine when melamine and formolite reaction, be preferably 0.7-2.5 weight %, the amount of the base catalyst that adds simultaneously with phenols and formaldehyde is generally the 2-10 weight % of phenols weight, is preferably 3-7 weight %.
As phenols, common available toluene, and other various alkyl phenols etc. also can use.These phenols can a kind of independent use, also can share more than 2 kinds.
The ratio of melamine and phenols, melamine is the 0.25-of phenols weight usually
For the outermost paper base material opposite with Copper Foil, with the bonding amount of melmac resin modified phenol resin with more than the 21 weight %, below the 25 weight % for well, during less than 21 weight %, can not get improving the effect of anti-silver-colored animal migration.And when surpassing 25 weight %, then influential to the punching processing characteristics.On the other hand, the bonding amount with the melmac resin modified phenol resin on other paper base materials is 15-20 weight %, and anti-silver-colored animal migration reduces during less than 15 weight %, then punching processing reduction when surpassing 20 weight %.
Dipping with the melmac resin modified phenol resin after the thermosetting resin of paper base material dipping can use phenolic resins, dry oil modified phenolic resin, unsaturated polyester resin etc.
Particularly, in order to obtain the good laminate of punching processing, can use dry oil modified phenolic resin satisfactorily.Make phenolic resin modified drying oil can use tung oil, dehydrated castor oil, linseed oil, Austria to carry west card wet goods; Phenols can use phenol, metacresol, paracresol, orthoresol, isopropyl-phenol, p-t-butyl phenol, to isopropenyl phenol paper polymers, nonyl phenol, bisphenol-A etc.
In the manufacture process of dry oil modified phenolic resin, normally make the reaction of drying oil and phenols earlier.The class reaction.
Amount with the drying oil of phenols reaction, the total amount of relative phenols and drying oil (for example tung oil), be generally 20-50 weight %, be preferably 25-40 weight %, if the amount of drying oil is discontented 20 weight %, punching processing, electric erosion resistance reduce, if surpass 50 weight %, then punching processing and intensity are all seen reduction.
The reaction temperature of phenols and drying oil reaction is generally 65-120 ℃, is preferably 70-100 ℃; Reaction time is generally 30-200 minute, is preferably 30-150 minute.This reaction can fully be carried out under normal pressure usually.Carry out preferable under the existence that is reflected at acidic catalysts such as p-methyl benzenesulfonic acid of this drying oil and phenols.Use under the situation of acidic catalyst, its consumption, the total amount with respect to phenols and drying oil (as tung oil) is generally 0.05-0.4 weight %, is preferably 0.05-0.3 weight %.
After above-mentioned reaction finishes, in reactant liquor, add formaldehyde and base catalyst, usually at 60-90 ℃, more fortunately 65-85 ℃, reacted 30-240 minute, be preferably 30-180 minute, obtain the principal component-drying oil modified phenolic resin of laminate of the present invention with drying oil modified phenolic resin composition.Again, this reaction can fully be carried out under normal pressure usually.
As formaldehyde source, available formalin, paraformaldehyde etc.The consumption of formaldehyde, common 1 mole of phenols 1.0-1.7 mole is preferably the 1.0-1.5 mole.
As base catalyst, available such as ammonia, hexa, trimethylamine, triethylamine etc.The consumption of base catalyst, common 1 mole of phenols 0.01-0.05 mole is preferably the 0.01-0.04 mole.
In order to improve the bonding strength with substrate, Copper Foil preferably uses and is adhering to adhesive.
In the present invention, except above-mentioned with melmac resin modified phenol resin and other thermosetting resins, as required, in order to give laminate with anti-flammability, also can be with brominated epoxy resin, anti-flammability compositions such as phosphoric acid ester such as bromides such as tetrabromobisphenol A diglycidyl ether, triphenyl phosphate, cresyl phosphate diphenyl ester mix use with thermosetting resin.The blended amount of anti-flammability composition, thermosetting resin 100 weight portions with respect to beyond the melmac resin modified phenol resin are generally the 5-100 weight portion, are preferably the 10-70 weight portion.
When making single side copper-clad laminate of the present invention, at first, make paper base material flood that above-mentioned three polyamino resin resin modified phenol resin are dissolved in the mixture of organic solvent, water or organic solvent and water and the lacquer that obtains (primary coat with lacquer), and drying.Organic solvent should be used the mixed solvent of methyl alcohol, toluene, methyl alcohol and toluene etc.Solid formation branch concentration in the lacquer (being dissolved in the total concentration that desolventizes composition in addition in the solvent) is advisable with 10-20 weight % usually.
In this case, prepare two kinds of the preforming materials that bonding amount with the melmac resin modified phenol resin is 21-25 weight % and 15-20 weight %.
Then, each preforming material dipping is above-mentioned to be dissolved in the lacquer (face is coated with lacquer) of organic solvent gained with the thermosetting resin beyond the melmac resin modified phenol resin, and drying, preforming material.Organic solvent should be used the mixed solvent of methyl alcohol, toluene, methyl alcohol and toluene etc.Solid formation branch concentration (being dissolved in the total concentration of the composition except that organic solvent in the organic solvent) in the lacquer is advisable with 50-80 weight % usually.
With the adhesive capacity of thermosetting resin on paper base material beyond the cyanurotriamide modified phenolic resin, so that the 40-65 weight % that all resins adhesive capacity (total amount of the composition in the preforming material beyond the paper base material) reaches usually with respect to the preforming material total amount in the preforming material is advisable, be preferably 45-60 weight %.
The preforming material and the Copper Foil that obtain are like this overlapped in the following order: Copper Foil, be the preforming material number of 15-20 weight %, be one of the preforming material of 21-25 weight % with melmac resin modified phenol resin adhesive capacity with melmac resin modified phenol resin adhesive capacity, heating pressurization more promptly obtains single side copper-clad laminate of the present invention.
The condition of heating pressurization, usually, heating-up temperature is 150-200 ℃, is preferably 160-190 ℃; Pressure 5-20MPa is preferably 9-15MPa; Time is 30-180 minute, is preferably 60-120 minute.
If many with the adhesive capacity of melmac resin modified phenol resin, the reaction of resin and paper base material just can fully be carried out, and the paper fiber can be topped by resin fully.Because silver ion moves along the paper fiber surface,, can suppress the silver migration so the paper fiber surface is complete when topped by resin.
The mobile moisture effects that also is subjected to moisture absorption of silver ion.The moisture of moisture absorption after a little while, silver ion moves difficulty.If the paper fiber surface is topped fully by resin, then moisture absorption also tails off.On the other hand, increase as if adhesive capacity, then the punching processing variation with the melmac resin modified phenol resin.But, moisture absorption mainly betides the surface, therefore defective during punching processing then easily betides circuit surface Copper Foil one side, only makes the outermost paper base material opposite with Copper Foil increase adhesive capacity with the melmac resin modified phenol resin, just can not sacrifice punching processing and suppresses the silver migration.The synthesis example primary coat is synthetic with lacquer
With formalin 240g, melamine 125g, trimethylamine 1.5g adds phenol 370g in reaction under 70 ℃ after 120 minutes again, formalin 350g, trimethylamine 20g was in 90 ℃ of reactions 30 minutes.After this, it is concentrated to reduce pressure, and removes condensation water and unreacted reactant, obtains with melmac resin modified phenol resin (melmac modification amount: 20 weight %).Add methyl alcohol and toluene mixed solvent (weight ratio 1/1) therein, obtain solid formation and divide coating with lacquer of 60 weight % with the melmac resin modified phenol resin.Face is coated with synthesizing with lacquer
Tung oil 35g, phenol 65g, p-methyl benzenesulfonic acid 0.1g after 60 minutes, are added paraformaldehyde 30g and ammoniacal liquor 5g in 80 ℃ of reactions again, in 70 ℃ of reactions 120 minutes.It is concentrated to reduce pressure then, obtains tung oil modified phenolic resin (tung oil-modified rate 35 weight %).To 100 parts of (weight portions of tung oil-modified phenolic resins, as follows), fusion triphenyl phosphate 28 weight portions, 20 parts of tetrabromobisphenol A diglycidyl ethers (epoxide equivalent 400), the mixed solvent (weight ratio 1/1) that adds methyl alcohol and toluene is made the tung oil modified phenolic resin lacquer that solid formation divides 60 weight %.
Embodiment 1
With brown paper (the heavy 125g/m of paper
2) the above-mentioned melmac phenol-formaldehyde resin modified lacquer of dipping, and dry.The resin adhesive capacity is two kinds of 22 weight % and 17 weight %.
Then, flood above-mentioned tung oil modified phenolic resin lacquer again, and drying, the preforming material that all resins adhesive capacity is 50-54 weight % obtained.
With the adhesive capacity of melmac phenol-formaldehyde resin modified is 7 overlappings of preformed of 17 weight %, Copper Foil (the copper thickness 35 μ m of attached adhesive on it, changing, adhesive thickness 30 μ m) 1, melmac phenol-formaldehyde resin modified adhesive capacity is the preforming material of 22 weight % on the opposition side of Copper Foil changes, heating pressurization (170 ℃, 9.8MPa, 90 minutes) obtains the single side copper-clad laminate of thickness 1.6mm.Embodiment 2
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is two kinds of 23 weight % and 18 weight %.
Then, carry out the dipping of above-mentioned tung oil modified phenolic resin similarly to Example 1, drying gets preforming material.
Get melmac phenol-formaldehyde resin modified adhesive capacity on the paper base material and be 7 of the preformed of 18 weight %, overlapping is got up, repeatedly go up Copper Foil (the copper thickness 35 μ m of attached adhesive above, adhesive thickness 30 μ m) 1, the opposition side of Copper Foil repeatedly on the paper base material melmac phenol-formaldehyde resin modified adhesive capacity be 1 of the preforming material of 23 weight %, heating is pressurizeed similarly to Example 1, obtains the single side copper-clad laminate of thickness 1.6mm.Embodiment 3
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is two kinds of 25 weight % and 18 weight %.
Then, carry out dipping, the drying of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
The adhesive capacity of getting melmac phenol-formaldehyde resin modified on the paper base material is 7 of the preforming materials of 18 weight %, overlapping is got up, the Copper Foil of repeatedly last attached adhesive is 1 above, the opposition side of Copper Foil repeatedly on the paper base material melmac phenol-formaldehyde resin modified adhesive capacity be 1 of the preforming material of 25 weight %, heating is pressurizeed similarly to Example 1, obtains the single side copper-clad laminate of thickness 1.6mm.Embodiment 4
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is two kinds of 21 weight % and 17 weight %.
Then, carry out the dipping of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
Get melmac phenol-formaldehyde resin modified adhesive capacity on the paper base material and be 7 of the preformed of 17 weight %, overlapping is got up, the Copper Foil of repeatedly last attached adhesive is 1 above, the opposition side of Copper Foil repeatedly on the paper base material melmac phenol-formaldehyde resin modified adhesive capacity be 1 of the preforming material of 21 weight %, heating is pressurizeed similarly to Example 1, obtains the single side copper-clad laminate of thickness 1.6mm.Comparative example 1
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is one kind of 17 weight %.
Then, carry out dipping, the drying of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
Get melmac phenol-formaldehyde resin modified adhesive capacity on the paper base material and be 8 of the preforming materials of 17 weight %, overlapping is got up, and repeatedly goes up 1 of the Copper Foil of attached adhesive above, and heating pressurization similarly to Example 1 obtains the single side copper-clad laminate of thickness 1.6mm.Comparative example 2
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is one kind of 22 weight %.
Then, carry out dipping, the drying of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
The adhesive capacity of getting melmac phenol-formaldehyde resin modified on the paper base material is 8 of the preforming materials of 22 weight %, and overlapping is got up, and repeatedly goes up 1 of the Copper Foil of attached adhesive above, and heating pressurization similarly to Example 1 obtains the single side copper-clad laminate of thickness 1.6mm.Comparative example 3
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is two kinds of 27 weight % and 18 weight %.
Then, carry out dipping, the drying of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
Get melmac phenol-formaldehyde resin modified adhesive capacity on the paper base material and be 7 of the preforming materials of 18 weight %, overlapping is got up, the Copper Foil of repeatedly last attached adhesive is 1 above, the opposition side of Copper Foil repeatedly on the paper base material melmac phenol-formaldehyde resin modified adhesive capacity be 1 of the preforming material of 27 weight %, heating is pressurizeed similarly to Example 1, obtains the single side copper-clad laminate of thickness 1.6mm.Comparative example 4
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is two kinds of 22 weight % and 17 weight %.
Then, carry out dipping, the drying of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
Get melmac phenol-formaldehyde resin modified adhesive capacity on the paper base material and be 7 of the preforming materials of 22 weight %, overlapping is got up, the Copper Foil of repeatedly last attached adhesive is 1 above, the opposition side of Copper Foil repeatedly on the paper base material melmac phenol-formaldehyde resin modified adhesive capacity be 1 of the preforming material of 17 weight %, heating is pressurizeed similarly to Example 1, obtains the single side copper-clad laminate of thickness 1.6mm.Comparative example 5
Brown paper is flooded above-mentioned melmac phenol-formaldehyde resin modified lacquer, drying.The resin adhesive capacity is two kinds of 22 weight % and 17 weight %.
Then, carry out dipping, the drying of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
The adhesive capacity of melmac phenol-formaldehyde resin modified on the paper base material of overlapping successively under 1 of the Copper Foil of attached adhesive is 3 of the preforming materials of 1 of preforming material, the 17 weight % of 4 of preformed, the 22 weight % of 17 weight %, heating is pressurizeed similarly to Example 1, obtains the single side copper-clad laminate of thickness 1.6mm.Comparative example 6 attached amounts are two kinds of 20 weight % and 17 weight %.
Then, carry out dipping, the drying of above-mentioned tung oil modified phenolic resin similarly to Example 1, get preforming material.
Get melmac phenol-formaldehyde resin modified adhesive capacity on the paper base material and be 7 of the preforming materials of 17 weight %, overlapping is got up, the Copper Foil of repeatedly last attached adhesive is 1 above, the opposition side of Copper Foil repeatedly on the paper base material melmac phenol-formaldehyde resin modified adhesive capacity be 1 of the preforming material of 20 weight %, heating is pressurizeed similarly to Example 1, obtains the single side copper-clad laminate of thickness 1.6mm.
For the single side copper-clad laminate of gained in the foregoing description and the comparative example, check its anti-silver migration and punching processing.It the results are shown in Table 1.
Table 1
Test method is as follows:
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Anti-silver-colored animal migration punching processing | ?2.3×10 9Very | ?2.8×10 9Very | ?3.3×10 9Very | ?1.0×10 9Very |
| Project | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 |
| Anti-silver-colored animal migration punching processing | ?4.1×10 7Very | ?6.3×10 9Difference | 3.8×10 9Poor slightly | ?4.2×10 7Difference | ?3.6×10 8Very | ?8.7×10 8Very |
1, anti-silver-colored animal migration
At pitch of holes 1.78mm, bonding land diameter 5mm, aperture 0.7mm are in the silver-colored migration test model of continuous 2 circuits in 90 holes, at relative humidity 90%RH, under 40 ℃ of the temperature, apply DC voltage 50V2000 hour continuously after, measure the resistance (unit: Ω) between circuit.
2, punching processing
Visual assessment is by pitch of holes 1.78mm, crackle between the hole during the 0.7mm punching processing of aperture.
Single side copper-clad laminate of the present invention, be on paper base material, to flood with melmac resin modified phenol resin, dry back heat of immersion thermosetting resin, and drying, the paper base material preforming material that obtains number in accordance with regulations overlaps, add one of the Copper Foil of attached adhesive in the one side, the single side copper-clad laminate that obtains through the heating pressurization; For each laminate, with the adhered resin amount of the phenolic resins of melmac sex change, on the outermost paper base material opposite with Copper Foil, be 21-25 weight %, on other paper base materials, be 15-20 weight %, therefore do not sacrifice punching processing and anti-silver-colored migration performance is good.
Claims (3)
1, single side copper-clad laminate, it is characterized in that: paper base material floods with the melmac resin modified phenol resin, and flood after drying with the thermosetting resin beyond the melmac resin modified phenol resin, dry then, the paper base material preforming material that obtains number in accordance with regulations overlaps, add one of Copper Foil in the one side, the heating pressurization obtains single side copper-clad laminate, for each paper base material, adhered resin amount with melmac modification De Fen Chuo resin, on the outermost paper base material opposite with Copper Foil, for paper base material with the 21-25 weight % of the total amount of melmac resin modified phenol resin, on other paper base materials, for paper base material with the 15-20 weight % of the total amount of melmac resin modified phenol resin.
2,, be phenolic resins or dry oil modified phenolic resin wherein with the thermosetting resin beyond the melmac resin modified phenol resin by the described single side copper-clad laminate of claim 1.
3,, be dry oil modified phenolic resin wherein with the thermosetting resin beyond the melmac phenol-formaldehyde resin modified by the described single side copper-clad laminate of claim 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP234576/94 | 1994-09-29 | ||
| JP23457694A JPH0890719A (en) | 1994-09-29 | 1994-09-29 | Single-sided copper clad laminated sheet |
| JP234576/1994 | 1994-09-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1129170A CN1129170A (en) | 1996-08-21 |
| CN1055434C true CN1055434C (en) | 2000-08-16 |
Family
ID=16973185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95115767A Expired - Fee Related CN1055434C (en) | 1994-09-29 | 1995-09-29 | Single side copper-clad laminate |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0890719A (en) |
| CN (1) | CN1055434C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010056135A (en) * | 2008-08-26 | 2010-03-11 | Japan Aviation Electronics Industry Ltd | Phenolic resin composition for wiring coating, printed circuit board using the same, and method of manufacturing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6234189A (en) * | 1985-08-08 | 1987-02-14 | 富士通株式会社 | Display unit |
| US4652324A (en) * | 1983-10-07 | 1987-03-24 | Sanyo-Kokusaku Pulp Co., Ltd. | Process for the production of laminated sheet |
| JPH04223113A (en) * | 1990-12-26 | 1992-08-13 | Hitachi Chem Co Ltd | Manufacture of laminated sheet |
-
1994
- 1994-09-29 JP JP23457694A patent/JPH0890719A/en active Pending
-
1995
- 1995-09-29 CN CN95115767A patent/CN1055434C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4652324A (en) * | 1983-10-07 | 1987-03-24 | Sanyo-Kokusaku Pulp Co., Ltd. | Process for the production of laminated sheet |
| JPS6234189A (en) * | 1985-08-08 | 1987-02-14 | 富士通株式会社 | Display unit |
| JPH04223113A (en) * | 1990-12-26 | 1992-08-13 | Hitachi Chem Co Ltd | Manufacture of laminated sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1129170A (en) | 1996-08-21 |
| JPH0890719A (en) | 1996-04-09 |
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