CN1119583A - Method of producing laminate - Google Patents
Method of producing laminate Download PDFInfo
- Publication number
- CN1119583A CN1119583A CN95105865A CN95105865A CN1119583A CN 1119583 A CN1119583 A CN 1119583A CN 95105865 A CN95105865 A CN 95105865A CN 95105865 A CN95105865 A CN 95105865A CN 1119583 A CN1119583 A CN 1119583A
- Authority
- CN
- China
- Prior art keywords
- phenolic resins
- dihydro
- modified
- benzoxazine colophony
- formaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000011094 fiberboard Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 57
- 229920001568 phenolic resin Polymers 0.000 claims description 45
- 239000005011 phenolic resin Substances 0.000 claims description 43
- -1 substituted-phenyl Chemical group 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000003825 pressing Methods 0.000 claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 150000003141 primary amines Chemical class 0.000 claims description 20
- 239000000123 paper Substances 0.000 claims description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011889 copper foil Substances 0.000 claims description 15
- 235000010678 Paulownia tomentosa Nutrition 0.000 claims description 12
- 240000002834 Paulownia tomentosa Species 0.000 claims description 12
- 238000007731 hot pressing Methods 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 229920001131 Pulp (paper) Polymers 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- ZVSFJDJJSJKZKM-UHFFFAOYSA-N C=O.NC(=O)N.C1=C(C=CC=C1O)C Chemical class C=O.NC(=O)N.C1=C(C=CC=C1O)C ZVSFJDJJSJKZKM-UHFFFAOYSA-N 0.000 claims 4
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 abstract description 36
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 36
- 239000001257 hydrogen Substances 0.000 description 36
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000002383 tung oil Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 150000002672 m-cresols Chemical class 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000010773 plant oil Substances 0.000 description 2
- 150000003142 primary aromatic amines Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 238000009288 screen filtration Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
Landscapes
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a production process of a laminated board. The process is to form dihydrogen-1, 3-benzoxazine resin which has at least two dihydrogen-1, 3-benzoxazine units in at least one piece of board, , to fold the board with at least one piece of baseplate of a fiberboard layer upon layer and form layered composite material, and to make the composite material into a laminated board by a pressure sintering, or to form at least one piece of fiberboard parent metal which has dihydrogen-1, 3 benzoxazine resin powder by the pressure sintering. The present invention has outstanding security and does no harm to the environment.
Description
The present invention relates to a kind of method of producing zone pressing plate, this laminate can be used as electrical insulating board, especially is used as the insulating base of printed circuit board (PCB).
Insulation board especially can be by applying with insulating resin impregnation of fibers plate substrate as the production of the laminate (hereinafter referred is a laminate) of the insulating base of printed circuit board (PCB), obtain the pre-preg plate thereby heat impregnated base material, then several pieces pre-preg plates of placing by pressure sintering heating and compacting stratiform.The main insulating resin that uses is a thermosetting resin, as phenolic resins epoxy resin or unsaturated polyester resin.
With applying in the process of method with insulating resin impregnation of fibers plate substrate, a large amount of solvents had been used.
Using a large amount of solvents to build with the process of insulating resin impregnation of fibers plate substrate and maintenance is used to prevent various danger (as catch fire or explode) and prevents equipment because of the environmental pollution that causes of solvent of evaporation by applying method.These equipment price costlinesses, thus production cost increased.
Known dihydro-1,3-benzoxazine compound can polymerization and curing under heating, and do not produce volatile accessory substance [referring to Japanese Patent Application Publication communique № .49-47378].But in laminated board production, it is used as the solution that is dissolved in certain solvent such as MEK.In addition, part is because the particularity of material contains dihydro-1, and the cured product of 3-benzoxazine compound does not also drop into practical application as the laminate of substrate.
The purpose of this invention is to provide a kind ofly at the solvent-free dihydro-1 that uses down, the 3-benzoxazine compound utilizes the compound can polymerization and curing and do not produce the method for the characteristic producing zone pressing plate of volatile byproducts.
The invention provides a kind of method of producing zone pressing plate, be included in to form in a slice at least and contain at least two dihydros-1 by following formula (I) expression, the dihydro-1 of 3-benzoxazine unit, the 3-benzoxazine colophony:
R wherein
1Be phenyl, substituted-phenyl, methyl or cyclohexyl, R
2It is methyl, ethyl or phenyl, with n be the integer of o-2, the substituting group of substituted-phenyl is a halogen, the alkyl of alkyl such as 1-10 carbon atom, or the alkoxyl of alkoxyl such as 1-10 carbon atom, thereby with this sheet and at least a slice fiberboard substrate stratiform repeatedly put and form laminar composite, and laminar composite is formed laminate by hot pressing.
The present invention also provides a kind of method that forms laminate, comprise that a slice contains dihydro-1 at least, the fiberboard substrate of 3-benzoxazine colophony powder forms laminate by hot pressing, dihydro-1 wherein, 3-benzoxazine colophony (hereinafter referred Er hydrogen benzoxazine colophony) contains at least two dihydros-1 by formula (1) expression, 3-benzoxazine unit (hereinafter this unit is called for short Er hydrogen benzoxazine unit).
The preparation that is used for two hydrogen benzoxazine colophonies of the present invention can make each molecule contain at least two hydroxyl phenylene groups, by following formula (3) expression and on the ortho position of at least one hydroxyl the compound of unsubstituted and primary amine and formaldehyde react, wherein the hydroxyl of every mole of hydroxyl phenylene is used the primary amine of 0.2-0.9 mole, and the consumption of formaldehyde is at least two times of mole of primary amine.Hydroxyl phenylene group represents with following reaction equation to the transformation of Er hydrogen benzoxazine unit:
R wherein
1, R
2As above define with n, and hydroxyl phenylene unsubstituted on the ortho position of at least one hydroxyl.
Particularly, contain at least two hydroxyl phenylenes (3) by primary amine and per molecule and on the ortho position of at least one hydroxyl, do not contain substituent compound that (hereinafter this compound is called as the " compound that contains active hydroxyl phenylene group.) mixture formed is injected towards and is heated to 70 ℃ or higher, be preferably in 70-100 ℃ the formaldehyde.The mixture that obtains is at 70-110 ℃, is preferably 90-100 ℃ of reaction 20 minutes to 2 hours down, and drying under reduced pressure under 120 ℃ or lower temperature obtains Er hydrogen benzoxazine colophony then.
Every mole of hydroxyl that contains the compound of active hydroxyl phenylene group is used the 0.2-0.9 mole, the primary amine of preferable 0.4-0.9 mole, and use at least 2 times, the formaldehyde of the mole of preferable 2.0-2.5 primary amine doubly is feasible.If primary amine is less than 0.2 mole, the number of the Er hydrogen benzoxazine unit in the compound that then obtains can descend, and the degree of cross linking of settable compound can be crossed the low cured product that consequently can not obtain having sufficient intensity.If greater than 0.9 mole,, descending greater than the softening or performance under 200 ℃ the temperature thereby cause then because the little extension of strand can cause the decline of the degree of cross linking.
Consumption with respect to the primary amine of the compound that contains active hydroxyl phenylene group can followingly obtain.The compound and the primary amine reaction that will contain the hydroxyl phenylene, the wherein primary amine of the mole same molar of all hydroxyls in use and the compound.The weight of the product that obtains according to reality calculates the quantity of the hydroxyl that reacts, the i.e. number of activity hydroxy in the compound that contains hydroxyl phenylene group.Calculate the quantity (mol ratio) of the primary amine that should use then according to the hydroxy number that reacts that obtains.
Contain the compound of at least two active hydroxyl phenylenes as per molecule, multiple compound with phenol nuclear is available.
Some examples of this compound comprise that phenolic resins is as (line style) novolac resin or phenol-formaldehyde A, the xylene resin of phenol improvement, alkyl phenolic resin, the phenolic resins of melamine improvement, the m-cresol resin of the phenolic resins of polybutadiene improvement and tung oil improvement.Compound does not contain substituting group on the ortho position of hydroxyl (crosslinked place takes place) be unrestricted, and still the aspect of performance from solidification products is desirable.Thereby, in the novolac resin situation, preferably using random novolac resin, its few of ortho position connection and molecular weight are relatively low.
Er hydrogen benzoxazine colophony is one group of compound, and each molecule has the active hydroxyl phenylene group of varying number.And aborning, heat-curable compounds is polymerization mutually partly.
The example of some primary amine comprises aliphatic primary amine, as methylamine, and aliphatic undersaturated primary amine such as allylamine, ester ring family's primary amine such as cyclohexylamine and primary aromatic amine such as aniline and substituted aniline.The substituent example of some of substituted aniline comprises: halogen, alkyl and alkoxyl.
When using aliphatic primary amine, the heat-curable compounds meeting rapid solidification that obtains, but the hear resistance of cured product is relatively poor relatively.On the other hand, primary aromatic amine such as aniline are desirable, although because the heat-curable compounds that obtains needs longer time solidification relatively, cured product has good hear resistance.
Thereby the Er hydrogen benzoxazine colophony that a part obtains like this is prepolymerizedly can control molded setting rate or melt viscosity, and this way meets the requirements, promptly at 80-180 ℃, preferable 120-160 ℃ following heat treated 5-120 minute, preferable 10-60 minute.
In the method for producing zone pressing plate, make a slice plate at least such as the two hydrogen benzoxazine colophonies that will obtain, plate and at least a fiberboard substrate are placed the formation laminar composite with stratiform, by hot pressing laminar composite is pressed into laminate again, can in Er hydrogen benzoxazine colophony, adds the thermosetting resin that other have been used for the producing zone pressing plate with B-stage form or cured product form.Some examples of this thermosetting resin comprise plant oil modified phenolic resins, epoxy resin, mylar, vinylester resin and polyimide resin.
Can also be with 100 parts by weight Er hydrogen benzoxazine colophony and 3-75 parts by weight, the mixture that preferable 10-50 parts by weight particle size is formed less than the toner of 150 μ m is made sheet material.This toner is to remove tinsel etc. obtains waste material and make in the leftover pieces of the laminate of printed circuit board (PCB) or clout by grinding, the printed circuit board (PCB) laminate of producing such as the plant oil modified phenolic resins of use or epoxy resin.In order to disperse, toner preferably has low particle size, is generally 100 μ m or littler, is more preferred from 1-50 μ m.Can be according to the necessary performance of printed circuit laminate and the composition of this resin compound is selected or improved.
Except above-mentioned additive, also can add plasticizer as required.
Use for example hot melt coating machine, by pressing on the sheet material and heating Er hydrogen benzoxazine colophony and the Er hydrogen benzoxazine that will obtain like this is applied on metallic plate or heat stable resin plate such as the fluorocarbon resin plate equably, form laminates.
Plate thickness depends on the material and the thickness of fiberboard substrate.The basic weight of plate (quantitatively) is preferably 120～200g/m
2, be more preferred from 140～180g/m
2
Being used for fiberboard substrate of the present invention can be any fiberboard substrate that is generally used for the producing zone pressing plate.Some examples comprise paper, the woven cloth of glass and glass nonwoven.
The thickness of fiberboard substrate is generally 0.1～0.5mm, is preferably 0.2～0.3mm.
Fiberboard substrate is preferably through preliminary treatment.For example, paper is with water soluble phenol resin or water miscible melamine-modified phenolic resins preliminary treatment, and vitreous material silane coupling agent preliminary treatment.
Will be at least a slice fiberboard substrate and at least a slice two hydrogen benzoxazine colophonies build up the formation laminar composite by stratiform, cover mold release film again, make laminate with pressure sintering then.Also can use a plurality of composite material sheets, wherein each all is attached to Er hydrogen benzoxazine colophony plate by hot rolling with fiberboard substrate and makes.In addition, can make continuously with Er hydrogen benzoxazine colophony coated fiber plate substrate.
Also can and make with tinsel such as the alternative mold release film of Copper Foil at laminate one-sided or the both sides clad metal.Although Copper Foil is often used as tinsel, also can use other tinsels, as nickel foil or aluminium foil according to desired properties.
With pressure sintering and in the method for producing zone pressing plate by forming a slice at least and containing the fiberboard substrate of two hydrogen benzoxazine colophony powder, after the Er hydrogen benzoxazine colophony that as above makes is ground into powder, powder and fibrous material are scattered in the water, be made into thin slice with wire screen filtration used in the papermaking, dry again, make the fiber sheet substrate that contains Er hydrogen benzoxazine colophony powder.In this case, as mentioned above, with a part of Er hydrogen benzoxazine colophony at 80～180 ℃, preferable 120～160 ℃ of following heat treatments 5～120 minutes, preferable 10～60 minutes and prepolymerization is favourable so that can control molded setting rate or melt viscosity.
Fibrous material is cellulose fibre preferably, but also can use inorganic short fiber such as staple glass fibre.
Also can use the dry production fiberboard substrate, wherein fiber be mixed the form of then mixture being laminated mutually with Er hydrogen benzoxazine colophony powder.
Er hydrogen benzoxazine colophony particles of powder chi is generally 300 μ m or littler for a short time, is preferably 50 μ m or littler, is more preferred from 10～50 μ m.The quantity of contained Er hydrogen benzoxazine colophony powder is preferably 3～75 weight % in the fiberboard substrate, is more preferred from 10～50 weight %, is benchmark with the gross weight of fiberboard substrate.If if quantity is less than 3 weight %, the moulding meeting is had any problem, but greater than 75%, then the laminate insufficient strength.
At least a slice fiberboard substrate (wherein being mixed with aforesaid two hydrogen benzoxazine powder) covers with mold release film, and makes laminate with pressure sintering.When using two or multi-disc fiber sheet substrate, these sheets are placed by stratiform.Also can and make with tinsel such as the alternative mold release film of Copper Foil at laminate one-sided or the both sides clad metal.Although Copper Foil is often used as tinsel, also can use other tinsels, as nickel foil or aluminium foil according to desired properties.
In the method for the fiberboard substrate that the method for using Er hydrogen benzoxazine colophony plate and use contain Er hydrogen benzoxazine colophony powder, hot pressing is usually 150～190 ℃ of temperature, and preferable 160～180 ℃, pressure 20～140kg/cm
2, preferable 60～110kg/cm
2Under carried out preferable 60～120 minutes 30～180 minutes.
Embodiment 1～13 and comparative example 1 and 2 embodiment 1
With 1.9kg phenol, 1.0kg formaldehyde (37% aqueous solution) and 4g oxalic acid add in 5 liters of retort, react 6 hours under reflux temperature again.Subsequently, reduction vaporization is removed unreacted phenol and water.The softening point of the resin that obtains is 84 ℃ (around-France and ball methods), and the ratio of (remaining phenol and contain the product of two phenyl ring)/(product that contains three or more phenyl ring) is 18/82 (ratio of the peak area that obtains with gel permeation chromatography).
Mix linear phenolic resin and 0.93kg10mol that 1.70kg (corresponding 16 moles of hydroxyls) obtains) aniline, stirred 5 hours at 80 ℃, make the solution mixture of homogeneous.In 5 liters of retort, add 1.62kg formaldehyde and be heated to 90 ℃, add the solution mixture of linear phenolic resin and aniline again.Reflux after 30 minutes, removed condensed water in 2 hours at 100 ℃ of reduction vaporizations.Obtain a kind of resin combination like this, wherein 71% activity hydroxy is converted to dihydro-1,3-benzoxazine unit.
The following calculating of the quantity of activity hydroxy.
Allow above-mentioned linear phenolic resin of 1.70kg (corresponding to the 16mol hydroxyl) and 1.49kg (16mol) aniline and 2.59kg formaldehyde by method reaction same as described above, whole activity hydroxies are transformed into dihydro-1,3-benzoxazine unit.Removing unreacted aniline, the output of the residue that stays after unreacted formaldehyde and the water, promptly the output of product Er hydrogen benzoxazine is 3.34kg.This means in the hydroxyl in linear phenolic resin that 14 moles of hydroxyls are transformed into dihydro-1,3-benzoxazine unit.
This means in the resin combination of Huo Deing, in the 14mol activity hydroxy, have 10mol (71%) to be converted to dihydro-1,3-benzoxazine unit in this embodiment.Embodiment 2
In 5 liters of retort, add 0.92kg and gather 1,2-butadiene (trade name: B-1000, by Nippon Soda Co., Ltd produces), 3.30kg phenol and 1g p-methyl benzenesulfonic acid are then 80 ℃ of reactions 5 hours.After cooling and washing, remove unreacted phenol with steam distillation, get the phenolic resins of 1.41kg polybutadiene-modified.According to the weight of the phenol that adds as calculated, the hydroxyl equivalent of the resin of acquisition is 270.
Repeat the program of embodiment 1, except using the phenolic resins of the polybutadiene-modified that 2.70kg (corresponding to the 10mol hydroxyl) obtains, 0.56kg (6mol) aniline and 0.97kg formaldehyde obtain a kind of resin combination, wherein 73% activity hydroxy is transformed into dihydro-1,3-benzoxazine unit.Embodiment 3
Add 0.50kg tung oil in 5 liters of retort, 4.00kg m-cresol and 4g p-methyl benzenesulfonic acid are then 80 ℃ of reactions 5 hours.After cooling and washing, remove unreacted m-cresol with steam distillation, get the tung oil-modified m-cresol aldehyde resin of 0.82kg.According to the weight of the m-cresol that adds as calculated, the hydroxyl equivalent of the resin of acquisition is 280.
Repeat the program of embodiment 1, except tung oil-modified m-cresol, the phenolic resins that uses 2.80kg (corresponding to the 10mol hydroxyl) to obtain, 0.56kg (6mol) aniline and 0.97kg formaldehyde, obtain a kind of resin combination, wherein 66% activity hydroxy is transformed into dihydro-1,3-benzoxazine unit.Embodiment 4
Adding 0.96kg xylene resin in 5 liters of retort (trade name: NIKANOLH, by Mitsubishi Gas Chemical.Co., Inc. produces, mean molecule quantity: 557, the active group equivalent: 96), 4.00kg phenolic resins and 4g p-methyl benzenesulfonic acid are then 80 ℃ of reactions 5 hours.After cooling and the washing, remove unreacted phenol, get the phenol-modified xylene resin of 1.12kg with steam distillation.According to the weight of unreacted phenol, the weight that calculates the phenol that replaces oxygen methylene (oxymethylene groups) is 0.31kg.This means that the hydroxyl equivalent of phenol-modified xylene resin is 340.
Repeat the program of embodiment 1, except the phenol-modified xylene resin that uses 3.40kg (corresponding to the 10mol hydroxyl) to obtain, 0.28kg (3mol) aniline and 0.49kg formaldehyde obtain a kind of resin combination, wherein 79% activity hydroxy is transformed into dihydro-1,3-benzoxazine unit.Embodiment 5 producing zone pressing plates 1
The linear phenolic aldehyde Er hydrogen benzoxazine colophony that obtains among the embodiment 1 flows through steel band then 115 ℃ of heating 20 minutes, and cooling forms thin slice.The basic weight of this sheet is 146g/m
2
Apply the thick brown paper of 0.2mm with water miscible melamine-modified phenolic resins, making resin content is 15 weight %.
The mutual stratiform of linear phenolic aldehyde two hydrogen benzoxazine colophony sheets that obtains among 8 brown paper of handling and 9 embodiment 1 is repeatedly put, and wherein two two hydrogen benzoxazine colophony sheets constitute outerly, and all place the thick Copper Foil of a slice 18 μ m on each skin.The laminar composite that obtains is placed in two terminal templates, rises with 8MPa at 170 ℃ then, with multiple stage compressor moulding by hot pressing 90 minutes, obtains laminate 1.Embodiment 6 producing zone pressing plates 2
As embodiment 5, the linear phenolic aldehyde two hydrogen benzoxazine colophonies that obtain among the heat treatment embodiment 1 fully mix with 20 weight % powder (is benchmark with two hydrogen benzoxazine colophonies) then.This powder is by (the FR-2 plate has been removed Copper Foil with paper-phenolic sheet.) to grind to form particle size be that 50 μ m or littler powder make.Mixture flows through steel band, and cooling again forms thin slice.The basic weight of this sheet is 146g/m
2
Subsequently, use the program producing zone pressing plate 2 same with producing zone pressing plate 1.Embodiment 7 producing zone pressing plates 3
Water-soluble melamine-modified phenolic resin is fully mixed with 10 weight % (is benchmark with water-soluble melamine-modified phenolic resins) powder.This powder is to make by paper-phenolic sheet (the FR-2 plate has been removed Copper Foil) is ground to form particle size 50 μ m or littler powder.Mixture is applied on the thick brown paper of 0.2mm, makes brown paper contain 15 weight % mixtures.Press the same mode producing zone pressing plate 3 of producing zone pressing plate among the embodiment 62, except the resin sheet of producing among the brown paper that uses such processing and the embodiment 6, promptly contain pouncing paper-phenolic sheet and the linear phenolic aldehyde Er hydrogen benzoxazine colophony plate of powder.Embodiment 8 producing zone pressing plates 4
It is thick to apply 0.2mm with water-soluble melamine-modified phenolic resins, contains the brown paper of 10 weight % powder, makes brown paper contain the resin of 15 weight %.This powder is by paper-phenolic sheet (FR-2 has removed Copper Foil) being ground to form particle size 50 μ m or littler powder is made.Press the same mode producing zone pressing plate 4 of producing zone pressing plate among the embodiment 62, except the resin sheet of producing among the brown paper that uses such processing and the embodiment 6, promptly contain pouncing paper-phenolic sheet and the linear phenolic aldehyde Er hydrogen benzoxazine colophony plate of powder.The comparative example 1
In the presence of acid catalyst, allow tung oil and phenol reactant.After adding 85% paraformaldehyde, allow mixture react in the presence of base catalyst and form phenol-formaldehyde A, promptly tung oil-modified percentage is 39% tung oil-modified phenolic resins.Phenolic resins that 100 parts by weight are tung oil-modified and 25 parts by weight tetrabromos are dissolved in the MEK for bisphenol-A-2 Synthesis of Oligo Ethylene Glycol, obtain impregnating varnish.
Apply the thick brown paper of 0.2mm with water-soluble melamine-modified phenolic resins, and dry, and making its resin content is 15 weight %.The brown paper of crossing with the impregnating varnish impregnation process makes paper contain contained resin in the 53 weight % lacquer, and is dry again and produce prepreg.
8 prepregs and 2 Copper Foil stratiforms that applied adhesive are repeatedly put, and at 170 ℃, the laminate of two sides coating copper was made laminar composite in 90 minutes in hot pressing under the 8MPa.
The laminate that obtains is heat-resisting through air, heat loss, and water absorbs and the test of anti-insulating properties.The results are shown in table 1.
The air hear resistance is with make the laminate required time representation of bubbling in 200 ℃ of driers.Heat loss is used in the weight that placement caused in 10 minutes in 200 ℃ of driers and reduces expression.Water absorbs the percentage be used in weight that 50 ℃ of heat treatments caused in 24 hours again increase after putting 24 hours under 23 ℃ in water and represents.In order to measure anti-insulating properties, in boiling water, placed 2 hours at each laminate of removal Copper Foil relief, in laminate, bore the hole of 2 diameter 5mm then, the spacing distance at its centre-to-centre spacing center is 15mm.Subsequently, in the hole, insert the taper pin of anti-insulation tester, measured anti-insulating properties in 1 minute by applying the 500V direct current.
Table 1
Embodiment 9-12 producing zone pressing plate 5～8
| Laminate 1 | Laminate 2 | Laminate 3 | Laminate 4 | The comparative example 1 | |
| Air hear resistance (min) | ????60 | ????45 | ????40 | ????38 | ????30 |
| Heat loss (%) | ????0.10 | ????0.18 | ????0.15 | ????0.20 | ????0.35 |
| Water absorbs (%) | ????0.65 | ????0.73 | ????0.70 | ????0.75 | ????0.70 |
| Anti-insulating properties (Ω) * 10 8 | ????5 | ????3 | ????1 | ????3 | ????2 |
With each all grinds to form 100 μ m or littler particle in 4 kinds of Er hydrogen benzoxazine colophonies that make among the embodiment 1～4,30% (weight) powder with paper pulp and paper pulp weight is scattered in the water then.Laminate with papermaking process again.The resin that obtains among the embodiment 1 is used for producing zone pressing plate 5, and the resin that obtains among the embodiment 2 is used for producing zone pressing plate 6, and the resin that obtains among the embodiment 3 is used for producing zone pressing plate 7, and the resin that obtains among the embodiment 4 is used for producing zone pressing plate 8.
7 sheets that obtain and the thick Copper Foil stratiform of a slice 18 μ m are repeatedly put.Laminar composite is placed between two terminal templates, with multiple stage compressor at 170 ℃, hot pressing 60 minutes under the 11MPa and moulding.Embodiment 13 producing zone pressing plates 9
The Er hydrogen benzoxazine colophony that obtains among the embodiment 1 is ground to form 100 μ m or littler powder.The paper pulp that to handle with water-soluble melamine-modified phenolic resins and the powder of paper pulp weight 30 weight % are soluble in water, then with the papermaking process form of laminating.
7 sheets that obtain and the thick Copper Foil stratiform of a slice 18 μ m are repeatedly put.Laminar composite is placed between two terminal templates, with multiple stage compressor at 170 ℃, hot pressing 60 minutes under the 11MPa and moulding.The comparative example 2
In the presence of acid catalyst, allow tung oil and phenol reactant.After adding 85% paraformaldehyde, allow mixture react in the presence of base catalyst and form phenol-formaldehyde A, promptly tung oil-modified percentage is 39% tung oil-modified phenolic resins.Phenolic resins that 100 parts by weight are tung oil-modified and 25 parts by weight tetrabromos are dissolved in the MEK for bisphenol-A-2 Synthesis of Oligo Ethylene Glycol, obtain impregnating varnish.
Apply the thick brown paper of 0.2mm with water-soluble melamine-modified phenolic resins, and dry, and making its resin content is 15 weight %.The brown paper of crossing with impregnation process makes paper contain contained resin in the 53 weight % lacquer, and is dry again and produce prepreg.
7 prepregs and 1 Copper Foil shape that applied adhesive are repeatedly put, and at 170 ℃, the laminate of single face coating copper was made laminar composite in 90 minutes in hot pressing under the 8MPa.
The laminate that obtains is heat-resisting through air, heat loss, and water absorbs and the test of anti-insulating properties.The results are shown in table 2.By testing with top identical mode.
Table 2
| Laminate 5 | Laminate 6 | Laminate 7 | Laminate 8 | Laminate 9 | The comparative example 2 | |
| Air hear resistance (min) | ????60 | ????45 | ????40 | ????40 | ????42 | ????30 |
| Heat loss (%) | ????0.16 | ????0.20 | ????0.21 | ????0.22 | ????0.20 | ????0.35 |
| Water absorbs (%) | ????0.65 | ????0.60 | ????0.61 | ????0.61 | ????0.35 | ????0.75 |
| Anti-insulating properties (Ω) * 10 8 | ????5 | ????4 | ????5 | ????5 | ????5 | ????2 |
The inventive method is being outstanding aspect security and the environmental sanitation.Because it has utilized the character of benzoxazine colophony, promptly this resin can solidify and not produce low-molecular-weight accessory substance, and it makes the production of laminate needn't use solvent.
Claims (17)
1. the method for a producing zone pressing plate is characterized in that, is included at least and forms dihydro-1 in a slice, and 3-benzoxazine colophony, this resin contain at least two dihydros-1 by following formula (1) expression, 3-benzoxazine unit
R wherein
1Be phenyl, substituted-phenyl, methyl or cyclohexyl, R
2Be methyl, ethyl or phenyl and n are 0～2 integers, the substituting group of substituted-phenyl is a halogen, alkyl or alkoxyl, thus with this sheet and at least a slice fiberboard substrate stratiform repeatedly put and form laminar composite, and laminar composite is formed laminate by hot pressing.
2. the method for claim 1 is characterized in that, also tinsel is positioned over the one side at least of laminar composite, and the reusable heat platen press is made laminate with the composite that obtains.
3. the method for claim 1, it is characterized in that, dihydro-1, the 3-benzoxazine colophony is to be selected from phenolic resins, the phenolic resins of polybutadiene-modified, the product of the primary amine of a kind of resin of tung oil-modified m-cresol urea formaldehyde and phenol-modified xylene resin and formaldehyde and following formula (2) expression:
R
1-NH
2(2) R wherein
1Be phenyl, substituted-phenyl, methyl or cyclohexyl.
4. method as claimed in claim 3 is characterized in that, dihydro-1,3-benzoxazine colophony are the product of phenolic resins and formaldehyde and primary amine.
5. method as claimed in claim 2, it is characterized in that dihydro-1,3-benzoxazine colophony are the product of phenolic resins and formaldehyde and aniline, fiberboard substrate is the paper material of handling with water-soluble melamine-modified phenolic resins, and metal forming is a Copper Foil.
6. the method for claim 1 is characterized in that, this sheet is that the mixture of 3-benzoxazine colophony and thermosetting powders is made with dihydro-1.
7. method as claimed in claim 6 is characterized in that, thermosetting powders is to grind insulating laminated sheet and the powder that makes.
8. method as claimed in claim 6, it is characterized in that this sheet is that the mixture of 3-benzoxazine colophony and thermosetting powders is made with dihydro-1, and also tinsel is placed the one side at least and the reusable heat platen press of laminar composite that the composite that obtains is made laminate.
9. method as claimed in claim 6, it is characterized in that, dihydro-1, the 3-benzoxazine colophony is to be selected from phenolic resins, the phenolic resins of polybutadiene-modified, the product of the primary amine of a kind of resin of tung oil-modified m-cresol urea formaldehyde and phenol-modified xylene resin and formaldehyde and formula (2) expression.
10. method as claimed in claim 9 is characterized in that, dihydro-1,3-benzoxazine colophony are the product of phenolic resins and formaldehyde and primary amine.
11. method as claimed in claim 7 is characterized in that, dihydro-1,3-benzoxazine colophony are the product of phenolic resins and formaldehyde and aniline, and fiberboard substrate is the paper material of handling with water-soluble melamine-modified phenolic resins.
12. the method for a producing zone pressing plate is characterized in that, comprise with pressure sintering will be at least a slice contain dihydro-1, the fiberboard substrate of 3-benzoxazine colophony is pressed into laminate, dihydro-1 wherein, 3-benzoxazine colophony contain at least two dihydros-1 by following formula (1) expression, 3-benzoxazine unit
R wherein
1Be phenyl, substituted-phenyl, methyl or cyclohexyl, R
2Be methyl, ethyl or phenyl and n are 0～2 integers, and the substituting group of substituted-phenyl is halogen, alkyl or alkoxyl.
13. method as claimed in claim 12 is characterized in that, the one side at least that tinsel is positioned over fiberboard substrate forms laminar composite, and the reusable heat platen press is made laminate with the composite that obtains.
14. method as claimed in claim 12, it is characterized in that, dihydro-1, the 3-benzoxazine colophony is to be selected from phenolic resins, the phenolic resins of polybutadiene-modified, the product of the primary amine of a kind of resin of tung oil-modified m-cresol urea formaldehyde and phenol-modified xylene resin and formaldehyde and following formula (2) expression:
R
1-NH
2(2) R wherein
1Be phenyl, substituted-phenyl, methyl or cyclohexyl.
15. method as claimed in claim 14 is characterized in that, dihydro-1,3-benzoxazine colophony are the product of phenolic resins and formaldehyde and primary amine.
16. method as claimed in claim 13, it is characterized in that, dihydro-1, the 3-benzoxazine colophony is to be selected from phenolic resins, the phenolic resins of polybutadiene-modified, a kind of resin of tung oil-modified m-cresol urea formaldehyde and phenol-modified xylene resin and the product of formaldehyde and aniline, fiberboard substrate is by paper pulp and dihydro-1, the powder of 3-benzoxazine colophony constitutes, and metal forming is a Copper Foil.
17. method as claimed in claim 16 is characterized in that, paper pulp is handled with water-soluble melamine-modified phenolic resins.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP129972/1994 | 1994-06-13 | ||
| JP12997394A JP3228003B2 (en) | 1994-06-13 | 1994-06-13 | Manufacturing method of laminated board |
| JP6-129973 | 1994-06-13 | ||
| JP12997294A JP3222689B2 (en) | 1994-06-13 | 1994-06-13 | Manufacturing method of laminated board |
| JP129973/1994 | 1994-06-13 | ||
| JP6-129972 | 1994-06-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1119583A true CN1119583A (en) | 1996-04-03 |
| CN1057728C CN1057728C (en) | 2000-10-25 |
Family
ID=26465212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95105865A Expired - Lifetime CN1057728C (en) | 1994-06-13 | 1995-06-09 | Method of producing laminate |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR0162709B1 (en) |
| CN (1) | CN1057728C (en) |
| MY (1) | MY138359A (en) |
| TW (1) | TW308566B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188538A (en) * | 2015-04-10 | 2016-12-07 | 台光电子材料股份有限公司 | modified benzoxazine resin, composition and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI395768B (en) * | 2009-12-18 | 2013-05-11 | Elite Material Co Ltd | Polymer Materials and Their Applications |
| KR20160003699U (en) | 2015-04-16 | 2016-10-26 | 양세영 | A case for receipt |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5330864A (en) * | 1976-09-03 | 1978-03-23 | Hitachi Ltd | Production of x-ray image intensifier |
| US4731426A (en) * | 1985-10-01 | 1988-03-15 | The Dow Chemical Company | Polymerization product from cyanate functional maleimide |
-
1995
- 1995-05-16 TW TW084104843A patent/TW308566B/zh not_active IP Right Cessation
- 1995-06-08 MY MYPI95001514A patent/MY138359A/en unknown
- 1995-06-09 CN CN95105865A patent/CN1057728C/en not_active Expired - Lifetime
- 1995-06-10 KR KR1019950015294A patent/KR0162709B1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188538A (en) * | 2015-04-10 | 2016-12-07 | 台光电子材料股份有限公司 | modified benzoxazine resin, composition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960000487A (en) | 1996-01-25 |
| KR0162709B1 (en) | 1998-12-15 |
| TW308566B (en) | 1997-06-21 |
| CN1057728C (en) | 2000-10-25 |
| MY138359A (en) | 2009-05-29 |
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