CN102093737B - Composition for copper foil-clad laminated sheet and copper foil-clad laminated sheet prepared from composition - Google Patents
Composition for copper foil-clad laminated sheet and copper foil-clad laminated sheet prepared from composition Download PDFInfo
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- CN102093737B CN102093737B CN201010573418A CN201010573418A CN102093737B CN 102093737 B CN102093737 B CN 102093737B CN 201010573418 A CN201010573418 A CN 201010573418A CN 201010573418 A CN201010573418 A CN 201010573418A CN 102093737 B CN102093737 B CN 102093737B
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Abstract
The invention relates to a composition for a copper foil-clad laminated sheet and a copper foil-clad laminated sheet prepared from the composition. The composition for the copper foil-clad laminated sheet comprises the following components: thermosetting resin, curing agent and aluminum hydroxide with a clad on the surface thereof, wherein the clad is inorganic clad, organic clad or a combination thereof. The alkali resistance of aluminum hydroxide is improved by cladding one or more layers of dense substance with stable chemical properties and high heat resistance on the surface of aluminum hydroxide, thus the alkali resistance of the composition is improved. The copper foil-clad laminated sheet prepared from the composition has good flame retardance and processibility, and good alkali resistance.
Description
Technical field
The present invention relates to the copper-clad plate field, particularly a kind of copper-clad laminate that is used for the compsn of copper-clad laminate and uses its making.
Background technology
White lake is fire-retardant filler commonly used in the copper-clad plate; Have fire-retardant, be prone to disperse, advantage such as processibility is good; But the alkali resistance of white lake is poor, has limited its addition in copper-clad plate, and heavy addition can influence the alkaline resistance properties of copper-clad plate without surface-treated white lake.Therefore, can be through coat the alkali resistance that one deck alkali resistance material improves white lake in surface of aluminum hydroxide.Surface coating technology has many pieces of bibliographical informations, and pertinent literature is following:
1, Ohmori coats with liquid phase deposition, has optimized the coating condition, through the hydrolysis of TEOS in 2-enanthol solution with SiO
2Be coated to the rhombohedral iron ore (Fe of spinel type
2O
3) on;
2, deep behaviour etc. is with liquid phase deposition preparation preparation TiO
2Particle surface coated Si O
2Nanometer film;
3, Zhang Yingyong Al (NO
3)
3To nanometer SiO
2The surface coats Al (NO
3)
3, coat result's demonstration and can improve nanometer SiO
2Dispersiveness;
4, Fisher has studied the SiO of different size
2Particle is at Al
2O
3On coating;
5, patent EP0960855A1 mentions white lake is handled through silane coupling agent;
Yet in the existing document that relates to surface coating technology, also the pertinent literature of not finding to utilize cladded aluminium hydroxides such as silicon-dioxide, more do not relate to document and patent that the white lake after the coating is used in copper-clad plate.
Summary of the invention
The object of the present invention is to provide a kind of compsn that is used for copper-clad laminate; Improve the alkali resistance of white lake through coat the fine and close chemical property of one deck material stable, high heat resistance in surface of aluminum hydroxide, thereby can improve the alkali resistance of the copper-clad plate of using it.
Another object of the present invention is to provide a kind of copper-clad laminate that uses the above-mentioned compsn that is used for copper-clad laminate to make, also have good alkali resistance when having excellent flame-retardant performance, processibility.
For realizing above-mentioned purpose, the present invention provides a kind of compsn that is used for copper-clad laminate, comprises that component is following: thermosetting resin, solidifying agent and surface have the white lake of coating layer, and wherein coating layer is inorganic coating layer, organic coating layer or both combinations.
Said coating layer accounts for the 0.1-20% of white lake gross weight.
Said white lake with coating layer accounts for the 0.1-70% of solids content weight ratio in total component.
Said inorganic coating layer is silicon-dioxide, titanium oxide or aluminum oxide etc.
Said organic coating layer is TEB 3K, trimeric cyanamide or Triple Pressed Stearic Acid etc.
Also comprise curing catalyst, be glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole, glyoxal ethyline, 2-phenylimidazole or 1 benzyl 2 methyl imidazole etc.
Also comprise solvent, it accounts for total component concentration is 0-70%.
Simultaneously; The present invention also provides a kind of copper-clad laminate that uses the above-mentioned compsn that is used for copper-clad laminate to make; It comprises: the prepreg that several are superimposed and be overlaid on the Copper Foil on several superimposed prepreg one or both sides; Each prepreg comprises that base-material reaches through the compsn that be used for copper-clad laminate of the dry postadhesion of impregnation on base-material; This compsn that is used for copper-clad laminate comprises that component is following: thermosetting resin, solidifying agent and surface have the white lake of coating layer, and wherein coating layer is inorganic coating layer, organic coating layer or both combinations.
Wherein, said white lake with coating layer accounts for the 0.1-70% of solids content weight ratio in total component.Coating layer accounts for the 0.1-20% of white lake gross weight.Said inorganic coating layer is silicon-dioxide, titanium oxide or aluminum oxide etc., and organic coating layer is TEB 3K, trimeric cyanamide or Triple Pressed Stearic Acid etc.
The said compsn that is used for copper-clad laminate also comprises curing catalyst, and this curing catalyst can be glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole, glyoxal ethyline, 2-phenylimidazole or 1 benzyl 2 methyl imidazole etc.Also comprise solvent, it accounts for total component concentration is 0-70%.
The invention has the beneficial effects as follows: the compsn that is used for copper-clad laminate of the present invention; Improve the alkali resistance of white lake through coat the fine and close chemical property of one deck material stable, high heat resistance in surface of aluminum hydroxide; Thereby can improve the alkali resistance of said composition; The copper-clad laminate that uses said composition to make also has good alkali resistance when having excellent flame-retardant performance, processibility.
Embodiment
The present invention provides a kind of compsn that is used for copper-clad laminate, and it comprises that component is following: thermosetting resin, solidifying agent and surface have the white lake of coating layer.
Wherein, Thermosetting resin adopts used thermosetting resin in the prior art; Can comprise bifunctional or polyfunctional epoxy resin; For the epoxy resin of bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type, biphenyl type epoxy resin, naphthalene based epoxy resin, alicyclic based epoxy resin, phenol-phenolic epoxy, ortho-cresol-phenolic aldehyde property epoxy, dihydroxyphenyl propane-phenolic epoxy, Resorcinol type epoxy resin, polyethylene glycol type epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, cyclopentadiene or two cyclic diolefines and phenols condensation resin, isocyanate-modified epoxy resin, glycidyl amine type epoxy resin, glycolylurea epoxide resin, through terpene modified epoxy resin, 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin, 10-(2; The 5-dihydroxy phenyl)-9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide modifying epoxy resin, and 10-(2; 9-dihydroxyl naphthyl)-9, the 10-dihydro-9-oxy is assorted-in 10-phospho hetero phenanthrene-10-oxide modifying epoxy resin etc. one or more.
White lake is as fire-retardant filler; Its use can effectively improve flame retardant resistance and processibility of obtained sheet material etc.; And in order to improve the alkali resistance of white lake; The present invention is stable in the chemical property that surface of aluminum hydroxide coats one deck densification through coating technology, the material of high heat resistance, forms the white lake with coating layer.Said white lake with coating layer accounts for the 0.1-70% of solids content weight ratio in total component, and coating layer accounts for the 0.1-20% of white lake gross weight.This coating layer is inorganic coating layer, organic coating layer or both combinations, and said inorganic coating layer is silicon-dioxide, titanium oxide or aluminum oxide etc., and organic coating layer is TEB 3K, trimeric cyanamide or Triple Pressed Stearic Acid etc.
Said solidifying agent is diethyl toluene diamine, Dyhard RU 100,4, one or more in 4-diaminodiphenylsulfone(DDS), resol, the three fluoro boron mono aminoethanes.Also comprise solidifying agent promotor, can be selected from glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole, glyoxal ethyline, 2-phenylimidazole, 1 benzyl 2 methyl imidazole or the like.
The present invention also comprises solvent, and its content accounts for the 0-70% of total components by weight.Solvent for use can be N, dinethylformamide, N, one or more in N-DEF, acetone, butanone, pimelinketone, EGME, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ETHYLE ACETATE.
The copper-clad laminate that the above-mentioned compsn that is used for copper-clad laminate of use of the present invention is made; It comprises: the prepreg that several are superimposed and be overlaid on the Copper Foil on several superimposed prepreg one or both sides, each prepreg comprise base-material and through the compsn that be used for copper-clad laminate of the dry postadhesion of impregnation on base-material.Wherein, this compsn that is used for copper-clad laminate comprises that component is following: thermosetting resin, solidifying agent and surface have the white lake of coating layer, and wherein coating layer is inorganic coating layer, organic coating layer or both combinations.Said white lake with coating layer accounts for the 0.1-70% of solids content weight ratio in total component.Coating layer accounts for the 0.1-20% of white lake gross weight.Said inorganic coating layer is silicon-dioxide, titanium oxide or aluminum oxide etc., and organic coating layer is TEB 3K, trimeric cyanamide or Triple Pressed Stearic Acid etc.The said compsn that is used for copper-clad laminate also comprises curing catalyst, and this curing catalyst can be glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole, glyoxal ethyline, 2-phenylimidazole or 1 benzyl 2 methyl imidazole etc.Also comprise solvent, it accounts for total component concentration is 0-70%.
When copper-clad laminate of the present invention is made, strongthener such as glasscloth are immersed in the compsn glue that is used for copper-clad laminate of the present invention, the strongthener that impregnation is good carries out heat drying in baking oven, process prepreg.It is superimposed that prepared prepreg is opened in peek, places Copper Foil on the two sides, and pressurized, heated promptly can be made into copper-clad laminate.
Its alkali resistance is surveyed in copper-clad plate to the above-mentioned compsn that is used for copper-clad laminate is processed, further gives to explain in detail and describe like following embodiment.
Now the embodiment of the invention is specified as follows, but the present invention is confined to scope of embodiments.
Embodiment 1
100 weight part brominated bisphenol a type epoxy resin (DOW Chemical, epoxy equivalent (weight) 435, bromine content 19%; ProductName DER530), 3 weight part Dyhard RU 100s, 0.05 weight part glyoxal ethyline (four countries change into), (inorganic coating layer is a silicon-dioxide to the inorganic cladded aluminium hydroxide of 40 weight parts; It is 5% that coating layer accounts for the white lake weight ratio), be dissolved in N, the N N; Be mixed with the glue of 65wt%, the impregnation glasscloth forms prepreg (prepreg) through behind the heat drying then; Copper Foil is placed on the two sides, and pressurized, heated is processed copper clad laminate (copper-clad laminate).
Embodiment 2
100 weight part brominated bisphenol a type epoxy resin (DOW Chemical, epoxy equivalent (weight) 435, bromine content 19%; ProductName DER530), 3 weight part Dyhard RU 100s, 0.05 weight part glyoxal ethyline (four countries change into), (organic coating layer is a trimeric cyanamide to the organic cladded aluminium hydroxide of 40 weight parts; The mass ratio that coating layer accounts for white lake is 5%), be dissolved in N, the N N; Be mixed with the glue of 65wt%, the impregnation glasscloth forms prepreg (prepreg) through behind the heat drying then; Copper Foil is placed on the two sides, and pressurized, heated is processed copper clad laminate.
Comparative example 1
100 weight part brominated bisphenol a type epoxy resin (DOW Chemical, epoxy equivalent (weight) 435, bromine content 19%, ProductName DER530), 3 weight part Dyhard RU 100s; 0.05 weight part glyoxal ethyline (four countries change into), 40 weight part white lakes are dissolved in N; The N N is mixed with the glue of 65wt%, then the impregnation glasscloth; Form prepreg (prepreg) through behind the heat drying, Copper Foil is placed on the two sides, and pressurized, heated is processed copper clad laminate.
The alkali resistance of table 1 embodiment 1-2 and comparative example 1 gained copper clad laminate
To sum up stating the result can know, embodiment 1-2 after alkali resistance test, no white point phenomenon, and comparative example 1 obviously has white point, the copper clad laminate of embodiment 1-2 gained has good alkali resistance.
The above; Be merely preferred embodiment of the present invention; For the person of ordinary skill of the art, can make other various corresponding changes and distortion, and all these changes and distortion all should belong to the protection domain of claim of the present invention according to technical scheme of the present invention and technical conceive.
Claims (6)
1. a compsn that is used for copper-clad laminate is characterized in that, comprises that component is following: thermosetting resin, solidifying agent and surface have the white lake of coating layer, and wherein coating layer is inorganic coating layer; Said inorganic coating layer is silicon-dioxide, titanium oxide or aluminum oxide; Said coating layer accounts for the 0.1-20% of white lake gross weight.
2. the compsn that is used for copper-clad laminate as claimed in claim 1 is characterized in that said white lake with coating layer accounts for the 0.1-70% of solids content weight ratio in total component.
3. the compsn that is used for copper-clad laminate as claimed in claim 1 is characterized in that, also comprises curing catalyst, is glyoxal ethyline, 2-ethyl-4 Methylimidazole, 2-phenylimidazole or 1 benzyl 2 methyl imidazole.
4. the compsn that is used for copper-clad laminate as claimed in claim 1 is characterized in that, also comprises solvent, and it accounts for total component concentration is 0-70%.
5. a use is used for the copper-clad laminate that the compsn of copper-clad laminate is made according to claim 1; It is characterized in that; It comprises: the prepreg that several are superimposed and be overlaid on the Copper Foil on several superimposed prepreg one or both sides, each prepreg comprise base-material and through the compsn that be used for copper-clad laminate of the dry postadhesion of impregnation on base-material.
6. copper-clad laminate as claimed in claim 5 is characterized in that said white lake with coating layer accounts for the 0.1-70% of solids content weight ratio in total component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010573418A CN102093737B (en) | 2010-12-03 | 2010-12-03 | Composition for copper foil-clad laminated sheet and copper foil-clad laminated sheet prepared from composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010573418A CN102093737B (en) | 2010-12-03 | 2010-12-03 | Composition for copper foil-clad laminated sheet and copper foil-clad laminated sheet prepared from composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102093737A CN102093737A (en) | 2011-06-15 |
| CN102093737B true CN102093737B (en) | 2012-10-10 |
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| CN201010573418A Active CN102093737B (en) | 2010-12-03 | 2010-12-03 | Composition for copper foil-clad laminated sheet and copper foil-clad laminated sheet prepared from composition |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109294496A (en) * | 2018-09-10 | 2019-02-01 | 南亚电子材料(昆山)有限公司 | It is a kind of for the heat resistance filler of copper-clad plate and for the resin combination of copper-clad plate |
| CN110588116A (en) * | 2019-09-04 | 2019-12-20 | 重庆德凯实业股份有限公司 | Flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board and preparation method thereof |
| CN112831095B (en) * | 2021-01-28 | 2023-05-26 | 广州市白云化工实业有限公司 | Acid-base resistant modified aluminum oxide heat conducting powder, heat conducting silicon rubber and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1832977A (en) * | 2003-08-07 | 2006-09-13 | 日本瑞翁株式会社 | Polymerizable composition and formed body thereof |
| CN101280125A (en) * | 2008-05-27 | 2008-10-08 | 阮建军 | Production method of superfine silicon powder for electronic grade low-heat expansion coefficient copper clad laminate |
| CN101457012A (en) * | 2008-12-31 | 2009-06-17 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
| CN101585955A (en) * | 2008-12-31 | 2009-11-25 | 广东生益科技股份有限公司 | Resin composition, resin-coated copper foil produced by same and copper-clad plate produced by utilizing resin-coated copper foil |
-
2010
- 2010-12-03 CN CN201010573418A patent/CN102093737B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1832977A (en) * | 2003-08-07 | 2006-09-13 | 日本瑞翁株式会社 | Polymerizable composition and formed body thereof |
| CN101280125A (en) * | 2008-05-27 | 2008-10-08 | 阮建军 | Production method of superfine silicon powder for electronic grade low-heat expansion coefficient copper clad laminate |
| CN101457012A (en) * | 2008-12-31 | 2009-06-17 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
| CN101585955A (en) * | 2008-12-31 | 2009-11-25 | 广东生益科技股份有限公司 | Resin composition, resin-coated copper foil produced by same and copper-clad plate produced by utilizing resin-coated copper foil |
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| CN102093737A (en) | 2011-06-15 |
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