CN100432170C - Resin composition and back glued superthin copper clad dielectric layer material with the composition - Google Patents
Resin composition and back glued superthin copper clad dielectric layer material with the composition Download PDFInfo
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- CN100432170C CN100432170C CNB031313965A CN03131396A CN100432170C CN 100432170 C CN100432170 C CN 100432170C CN B031313965 A CNB031313965 A CN B031313965A CN 03131396 A CN03131396 A CN 03131396A CN 100432170 C CN100432170 C CN 100432170C
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Abstract
The present invention relates to a resin composition which comprises 0.5 to 25 portions by weight of adhesion macromolecular compounds, 10 to 45 portions by weight of resin comprising bromine, 10 to 60 portions by weight of epoxy resin and 5 to 35 portions by weight of stiffening agent. The resin composition can be added with organic solvent and is mixed into varnish, and the varnish is coated on an ultrathin copper foil to form a dielectric layer.
Description
Technical field
The present invention relates to a kind of resin combination, and contain the gum extra thin copper foil dielectric layer material of this resin combination.
Background technology
At present electronic product is sent out commentaries on classics towards compact, high-performance and portability direction, makes encapsulation, printed circuit board (PCB) downstream industries such as (PCB), and to technology and material aspect, all requirement must be satisfied the characteristic of high-density, high-reliability.
Traditional PCB is made of glass cloth, resin and Copper Foil.Because substrate contains glass cloth, so when using Laser drill machine drill hole, to cause micro molding not good, and technology is complicated, cost is higher, so advanced technology country progressively uses RCC Technology (" ResinCoated Copper ", gum Copper Foil) now, can save glass cloth and contain the resin pickup formality, not only simplify technology and can reduce cost, reduce weight, use in portable products such as notebook computer, mobile telephone, PDA in a large number at present.
In addition, as the copper foil material of electric power and signal conductor, for asking the high-density graph thinning, with the copper thickness thinning, be trend with no alternative, thus thickness from before 18 μ m or 35 μ m reduce to present 3 to 6 μ m, be referred to as extra thin copper foil (ultra thin copper foil).
General ultrafine gum Copper Foil, be to utilize aluminium foil as carrier, doing suitable surperficial pre-treatment and separating layer (or being called bonding coat) then on aluminium foil handles, the thick copper foil layer of 3 to the 6 μ m of re-plating afterwards, handle through alligatoring, heat resistanceheat resistant and anti oxidation layer, be coated with varnish again to form dielectric layer (dielectric layer), will carry aluminium foil at last and tear off.This ultra-thin gum Copper Foil is applicable on PCB and surface-mounted integrated circuit (" the IC ") support plate.But, present commercially available ultra-thin gum Copper Foil, it is too crisp generally to face dielectric layer, and heat impedance is not good, contacts shortcomings such as effect is bad with extra thin copper foil.
Copper clad laminate need possess the demand of high tenacity and high thermal resistance, with prior art, can cause substrate easily crisp as removing glass cloth to reach the frivolous purpose of substrate; How to remove glass cloth simultaneously again to keep the function of substrate, become the problem that industry seeks to solve.
This case the contriver find through broad research, resin combination with some specific component, add organic solvent and be modulated into varnish, coat on the Copper Foil (conductive layer), can form a dielectric layer to replace glass fibre adhesive plaster (prepreg), one can save glass cloth, and two can be high temperature resistant, and toughness is strong, is applicable to various circuit layout.Use the printed circuit board (PCB) of this ultra-thin gum copper clad laminate technology, thinner more than 1/2nd on the thickness than traditional printing circuit card, and because the simplification of technology and material, so can significantly reduce cost.
Summary of the invention
The object of the present invention is to provide a kind of resin combination.
Another object of the present invention is to provide a kind of gum extra thin copper foil dielectric layer material that contains this resin combination.
Embodiment
The invention provides a kind of resin combination, it comprises: (a) the adhesion macromolecular compound of 0.5 to 25 parts by weight (" binder polymer "); (b) the brominated resin of 10 to 45 parts by weight; (c) Resins, epoxy of 10 to 60 parts by weight; Reach (d) stiffening agent of 5 to 35 parts by weight.
Can be used for the adhesion macromolecular compound in the resin combination of the present invention, preferable content is between 5 to 15 weight parts, and its molecular-weight average is between 5,000 to 100,000.
Employed adhesion macromolecular compound there is no particular restriction in the resin combination of the present invention, can be used for adhesion macromolecular compound of the present invention for example can be, but be not limited to mix polybutadiene rubber (" mixed polybutadiene rubber "), vibrin (" polyester "), acrylic resin (" acrylic resin ") and polyamine base benzoic acid resin (" polyurethane "), and the mixture of these macromolecular compounds etc.
Can be used for the brominated resin in the resin combination of the present invention, its brominated ratio in this resin combination gross weight, is to be 5 to 25 weight %.
Employed brominated resin there is no particular restriction in the resin combination of the present invention, can be used for brominated resin of the present invention and for example can be, but be not limited to brominated Resins, epoxy, brominated vibrin and breathe out dragon (" Halons ") and composition thereof etc.
Can be used for the Resins, epoxy in the resin combination of the present invention, preferable content is between 15 to 30 weight parts.
Employed Resins, epoxy in the resin combination of the present invention is to comprise at least aly to have high glass transition temp (wherein this high glass transition temp is meant more than 100 ℃ for " glass-transition temperature ", Tg) person.
Employed Resins, epoxy is for containing two or a plurality of functional groups' Resins, epoxy in the resin combination of the present invention, it for example can be, but is not limited to bis-phenol (" bisphenol ") Resins, epoxy, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type novolac epoxy, phenol aldehyde type alkyl phenolic Resins, epoxy, modification (Modified) novolac epoxy, dicyclopentadiene (" dicyclopentadiene ") Resins, epoxy or its mixture.
Can be used for the stiffening agent in the resin combination of the present invention, preferable content is between 17 to 25 weight parts.
Employed stiffening agent is a those skilled in the art institute well known in the resin combination of the present invention, and its limiting examples comprises: amine-containing compound, guanidine class (" guanidine ") stiffening agent and imidazoles (" imidazole ") stiffening agent.
Resin combination of the present invention can optionally comprise additive known to those skilled in the art, and these additives for example can be defoamer (Defoaming Agent), flow agent (LevellingAgent), adhesion promotor (Adhesive Promoter), silane coupling agent (Silane CouplingAgent) or its mixture etc.
The present invention provides a kind of gum extra thin copper foil dielectric layer material in addition, and it comprises above-mentioned resin combination and organic solvent.
Gum extra thin copper foil dielectric layer material of the present invention when the content of adhesion macromolecular compound is lower than 0.5 weight part, then can't reach good contact effect with extra thin copper foil, and when so surpassing 25 weight parts as if content, then anti-chemical drug is not good; When the content of brominated resin was lower than 10 weight parts, then flame resistivity can reduce; When the content of Resins, epoxy was lower than 10 weight parts, then heat impedance can significantly reduce, and is right when if content surpasses 60 weight parts, then dielectric layer become fragile, the re-workability difficulty; And when the content of stiffening agent was lower than 5 weight parts, then heat impedance reduced, and when so surpassing 35 weight parts as if content, then anti-chemical drug can descend.
Be applicable to that the organic solvent in the dielectric layer material of the present invention there is no particular restriction, only need to dissolve above-mentioned resin combination person and get final product that the example includes, but are not limited to methyl alcohol, acetone, methylethylketone or toluene or its mixture etc.
Embodiment
Following examples will the present invention is described further, is not in order to limiting the scope of the invention, and any those skilled in the art without prejudice to spirit of the present invention following modification of being reached and variation, all belong to scope of the present invention.
Embodiment 1
The carboxyl-terminated butadiene propylene of 15 weight parts (Carboxyl Terminated ButadieneAcrylonitrile, CTBN) (1072CG, south Supreme Being's rubber) be composition a, the brominated Resins, epoxy of 25 weight parts (epoxy equivalent (weight)=499, softening point temperature is 75 ℃, brominated amount is 21wt.%, YDB-500, Toto chemical Industry, Co., Ltd.) be composition b, (epoxy equivalent (weight)=2000 and softening temperature are 124 ℃ to 10 weight part bisphenol-A Resins, epoxy, Epicion7051, Dai-Nippon Ink Chemistry, Co., Ltd.) (epoxy equivalent (weight)=215 and softening temperature are 78 ℃ with 15 weight part cresols-phenol aldehyde types (" cresol-novolac type ") Resins, epoxy, Epicion N-673, Dai-Nippon Ink Chemistry, Co. Ltd.) is composition c, with above-mentioned resin dissolves in methylethylketone (solvent), add 30 portions of amine by weight compounds (diamines phenylbenzene " Diamine Diphenyl Sulfone ", DDS) and 2 weight parts (2-ethyl-4-methylimidazole 2-E4MZ) is ingredient d, the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain varnish.
Comparative example 1
CTBN (the 1072CG of 15 weight parts, south Supreme Being's rubber) be composition a, (epoxy equivalent (weight)=2000 and softening temperature are 124 ℃ to 10 weight part bisphenol A type epoxy resins, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd.) (epoxy equivalent (weight)=215 and softening temperature are 78 ℃, Epicion N-673, Dai-Nippon InkChemistry with the novolac epoxy of 15 weight part cresols-phenol aldehyde types, Co., Ltd.) be composition c, in methylethylketone, adding 30 portions of amine by weight compounds (DDS) and 2 weight part 2-E4MZ is ingredient d with above-mentioned resin dissolves, the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain varnish.
Embodiment 2
CTBN (the 1072CG of 10 weight parts, south Supreme Being's rubber) be composition a, the brominated Resins, epoxy of 35 weight parts (epoxy equivalent (weight)=499, softening point temperature is 75 ℃, brominated amount is 21 weight %, YDB-500, Toto Chemical Industry, Co., Ltd.) be composition b, (epoxy equivalent (weight)=2000 and softening temperature are 124 ℃ to 15 weight part bisphenol A type epoxy resins, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd.) (epoxy equivalent (weight)=215 and softening temperature are 78 ℃ with 20 weight part cresols-phenol aldehyde type epoxy resins, Epicion N-673, Dai-Nippon InkChemistry, Co. Ltd.) is composition c, with above-mentioned resin dissolves in methylethylketone, adding 15 portions of amine by weight compounds (DDS) and 2 weight part 2-E4MZ is ingredient d, and the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain varnish.
Comparative example 2
Brominated Resins, epoxy (epoxy equivalent (weight)=499 of 35 weight parts, softening point temperature is 75 ℃, brominated amount is 21 weight %, YDB-500, Toto Chemical Industry, Co. Ltd.) is composition b, 15 weight part bisphenol A type epoxy resin (epoxy equivalent (weight)=2000, softening temperature is 124 ℃, and Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd.) (epoxy equivalent (weight)=215 and softening temperature are 78 ℃, Epicion N-673, Dai-Nippon Ink Chemistry with 20 weight part cresols-phenol aldehyde type epoxy resins, Co., Ltd.) be composition c, in methylethylketone, adding 15 portions of amine by weight compounds (DDS) and 2 weight part 2-E4MZ is ingredient d with above-mentioned resin dissolves, the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain varnish.
Comparative example 2-1
CTBN (the 1072CG of 30 weight parts, south Supreme Being's rubber) be composition a, the brominated Resins, epoxy of 35 weight parts (epoxy equivalent (weight)=499, softening point temperature is 75 ℃, brominated amount is 21 weight %, YDB-500, Toto Chemical Industry, Co., Ltd.) be composition b, (epoxy equivalent (weight)=2000 and softening temperature are 124 ℃ to 15 weight part bisphenol A type epoxy resins, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd.) (epoxy equivalent (weight)=215 and softening temperature are 78 ℃ with 20 weight part cresols-phenol aldehyde type epoxy resins, Epicion N-673, Dai-Nippon InkChemistry, Co. Ltd.) is composition c, above-mentioned resin is dissolved in the methylethylketone, adding 15 portions of amine by weight compounds (DDS) and 2 weight part 2-E4MZ is ingredient d, and the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain varnish.
Embodiment 3
CTBN (the 1072CG of 15 weight parts, south Supreme Being's rubber) be composition a, the brominated Resins, epoxy of 40 weight parts (epoxy equivalent (weight)=499, softening point temperature is 75 ℃, brominated amount is 21 weight %, YDB-500, Toto chemical Industry, Co., Ltd.) be composition b, (epoxy equivalent (weight)=2000 and softening temperature are 124 ℃ to 20 weight part bisphenol A type epoxy resins, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd.) (epoxy equivalent (weight)=215 and softening temperature are 78 ℃ with 25 weight part cresols-phenol aldehyde type epoxy resins, Epicion N-673, Dai-Nippon InkChemistry, Co. Ltd.) is composition c, above-mentioned resin is dissolved in the methylethylketone, adding 20 portions of amine by weight compounds (DDS) and 2 weight part 2-E4MZ is ingredient d, and the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain tackiness agent varnish.
Comparative example 3
CTBN (the 1072CG of 15 weight parts, south Supreme Being's rubber) be composition a, the brominated Resins, epoxy of 40 weight parts (epoxy equivalent (weight)=499, softening point temperature is 75 ℃, brominated amount is 21 weight %, YDB-500, Toto Chemical Industry, Co., Ltd.) be composition b, (epoxy equivalent (weight)=215 and softening temperature are 78 ℃ to 25 weight part cresols-phenol aldehyde type epoxy resins, Epicion N-673, Dai-Nippon Ink Chemistry, Co. Ltd.) is composition c, above-mentioned resin is dissolved in the methylethylketone, adding 20 portions of amine by weight compounds (DDS) and 2 weight part 2-E4MZ is ingredient d, and the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain tackiness agent varnish.
Comparative example 3-1
CTBN (the 1072CG of 15 weight parts, south Supreme Being's rubber) be composition a, the brominated Resins, epoxy of 40 weight parts (epoxy equivalent (weight)=499, softening point temperature is 75 ℃, brominated amount is 21 weight %, YDB-500, Toto Chemical Industry, Co., Ltd.) be composition b, (epoxy equivalent (weight)=2000 and softening temperature are 124 ℃ to 20 weight part bisphenol A type epoxy resins, Epicion 7051, Dai-Nippon Ink Chemistry, Co., Ltd.) (epoxy equivalent (weight)=215 and softening temperature are 78 ℃ with 25 weight part cresols-phenol aldehyde type epoxy resins, Epicion N-673, Dai-Nippon InkChemistry, Co. Ltd.) is composition c, above-mentioned resin is dissolved in the methylethylketone, adding 40 portions of amine by weight compounds (DDS) and 2 weight part 2-E4MZ is ingredient d, and the adhesion promotor of the flow agent of 2 weight parts and 4 weight parts can obtain tackiness agent varnish.
The varnish that the foregoing description and comparative example are modulated into, coat on the anti oxidation layer uneven surface of extra thin copper foil (thickness is 3 μ m or 6 μ m), drying is 10 minutes under 80 to 100 ℃ of temperature, make glue thickness at 60 to 80 μ m, make the gum extra thin copper foil, according to the ASTM standard, test flame resistivity, anti-chemical drug and stripping strength.The gained result is as shown in table 1.
Table 1
Conclusion:
1. the test result of comparing embodiment 1 and comparative example 1 is added the flame resistivity that brominated Resins, epoxy can increase the gum extra thin copper foil as can be known.
2. the test result of comparing embodiment 2 and comparative example 2 is added the adhesion macromolecular compound as can be known, can make the stripping strength of gum extra thin copper foil after pressing become big, has preferable then effect.
3. the test result of comparing embodiment 2 and comparative example 2-1 is added excessive adhesion macromolecular compound as can be known, though can increase stripping strength, anti-chemical drug can reduce, and can cause gummosis too fast and the not good problem of filling perforation arranged.
4. the test result of comparing embodiment 3 and comparative example 3 is not added the Resins, epoxy that softening point temperature is higher than pressing-in temp as can be known, and then the gum extra thin copper foil carries out can producing the too fast phenomenon of gummosis in the pressing process, is unfavorable for filling perforation.
5. the test result of comparing embodiment 3 and comparative example 3-1 is added excessive stiffening agent as can be known, and then anti-chemical drug can reduce.
Claims (15)
1. resin combination, it comprises:
(a) the adhesion macromolecular compound of 0.5 to 25 weight part;
(b) the brominated resin of 10 to 45 weight parts;
(c) 25 to 60 parts by weight of epoxy resin; And
(d) 5 to 35 weight part stiffening agents.
2. composition as claimed in claim 1, the high molecular content of wherein should adhering is between 5 to 15 weight parts.
3. composition as claimed in claim 1, the high molecular molecular-weight average of wherein should adhering is between 5,000 to 100,000.
4. composition as claimed in claim 1, wherein this adhesion polymer is selected from and mixes polybutadiene rubber, vibrin, acrylic resin and polyamine base benzoic acid resin and composition thereof.
5. composition as claimed in claim 1, wherein the brominated ratio of this brominated resin in this resin combination gross weight, is 5 to 20 weight %.
6. composition as claimed in claim 1, wherein this brominated resin is to be selected from brominated Resins, epoxy, brominated vibrin and to breathe out dragon and composition thereof.
7. composition as claimed in claim 1, wherein the content of this Resins, epoxy is between 25 to 30 weight parts.
8. composition as claimed in claim 1, wherein this Resins, epoxy comprises at least a glass transition temp at the resin more than 100 ℃.
9. composition as claimed in claim 1, wherein this Resins, epoxy is for containing two or a plurality of functional groups' Resins, epoxy.
10. composition as claimed in claim 9, wherein this contain two or a plurality of functional groups' Resins, epoxy be selected from bisphenol epoxy, bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenol aldehyde type novolac epoxy, phenol aldehyde type alkyl phenolic Resins, epoxy, modified phenolic Resins, epoxy and dicyclopentadiene Resins, epoxy and composition thereof.
11. composition as claimed in claim 1, wherein the content of this stiffening agent is between 17 to 25 weight parts.
12. composition as claimed in claim 1, wherein this stiffening agent is selected from amine-containing compound, guanidine class stiffening agent and imidazole hardeners and composition thereof.
13. composition as claimed in claim 1, it further comprises the additive that is selected from defoamer, flow agent, adhesion promotor and silane coupling agent and composition thereof.
14. a gum extra thin copper foil dielectric layer material is characterized in that comprising as each resin combination and organic solvent in the claim 1 to 13.
15. as the dielectric layer material of claim 14, wherein this organic solvent is methyl alcohol, acetone, methylethylketone or toluene or its mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031313965A CN100432170C (en) | 2003-05-20 | 2003-05-20 | Resin composition and back glued superthin copper clad dielectric layer material with the composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031313965A CN100432170C (en) | 2003-05-20 | 2003-05-20 | Resin composition and back glued superthin copper clad dielectric layer material with the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1548490A CN1548490A (en) | 2004-11-24 |
| CN100432170C true CN100432170C (en) | 2008-11-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031313965A Expired - Lifetime CN100432170C (en) | 2003-05-20 | 2003-05-20 | Resin composition and back glued superthin copper clad dielectric layer material with the composition |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI449745B (en) * | 2008-12-22 | 2014-08-21 | Iteq Corp | Bonding sheet and resin composition for preparing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134431B (en) * | 2010-01-22 | 2013-06-05 | 南亚塑胶工业股份有限公司 | Low dielectric resin varnish composition for laminated board and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050730A (en) * | 1989-10-06 | 1991-04-17 | 通用电气公司 | Polyphenylene oxide-hybrid epoxy resin system as laminates |
| WO1994012345A1 (en) * | 1992-11-30 | 1994-06-09 | Allied-Signal Inc. | A system of electronic laminates with improved registration properties |
| JPH06306147A (en) * | 1993-04-21 | 1994-11-01 | Showa Highpolymer Co Ltd | High-molecular unsaturated polymer resin composition and use thereof |
| CN1289352A (en) * | 1998-02-05 | 2001-03-28 | 美国3M公司 | Adhesive composition and precursor thereof |
| CN1405259A (en) * | 2001-12-18 | 2003-03-26 | 黄堂杰 | Adhensive for producing flexible printed circuit board base board and preparation method thereof |
-
2003
- 2003-05-20 CN CNB031313965A patent/CN100432170C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050730A (en) * | 1989-10-06 | 1991-04-17 | 通用电气公司 | Polyphenylene oxide-hybrid epoxy resin system as laminates |
| WO1994012345A1 (en) * | 1992-11-30 | 1994-06-09 | Allied-Signal Inc. | A system of electronic laminates with improved registration properties |
| JPH06306147A (en) * | 1993-04-21 | 1994-11-01 | Showa Highpolymer Co Ltd | High-molecular unsaturated polymer resin composition and use thereof |
| CN1289352A (en) * | 1998-02-05 | 2001-03-28 | 美国3M公司 | Adhesive composition and precursor thereof |
| CN1405259A (en) * | 2001-12-18 | 2003-03-26 | 黄堂杰 | Adhensive for producing flexible printed circuit board base board and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI449745B (en) * | 2008-12-22 | 2014-08-21 | Iteq Corp | Bonding sheet and resin composition for preparing the same |
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| Publication number | Publication date |
|---|---|
| CN1548490A (en) | 2004-11-24 |
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Address after: Kaohsiung City, Taiwan, China Patentee after: ETERNAL MATERIALS CO.,LTD. Address before: Kaohsiung City, Taiwan, China Patentee before: ETERNAL CHEMICAL CO.,LTD. |
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