CN102702989A - Cover film for flexible copper clad plate and preparation method thereof - Google Patents
Cover film for flexible copper clad plate and preparation method thereof Download PDFInfo
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- CN102702989A CN102702989A CN201210168343XA CN201210168343A CN102702989A CN 102702989 A CN102702989 A CN 102702989A CN 201210168343X A CN201210168343X A CN 201210168343XA CN 201210168343 A CN201210168343 A CN 201210168343A CN 102702989 A CN102702989 A CN 102702989A
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Abstract
The invention discloses a cover film for a flexible copper clad plate which has high heat resistance, flame resistance, electrical insulation property, excellent appearance and radiation protection property and preparation method thereof. The cover film for flexible copper clad plate is composited by an adhesive and release paper. The adhesive is composed of the following components in weight percentages of the raw materials: 30-40 parts of solvent type epoxy resin, 10-20 parts of solvent type epoxy toughening agent, 6-25 parts of halogen-free flame retardant, 1-3 parts of radiation protection agent, 1-3 parts of additive agent, 20-40 parts of solvent I, wherein the solvent type epoxy resin is obtained in a way that dissolving halogen-free epoxy resin and a solvent II are completely dissolved by mass ratio of 100:50-200. The solvent type epoxy toughening agent is obtained in a way that the epoxy toughening agent and a solvent III are completely dissolved by mass ratio of 100:250-700.
Description
Technical field
The present invention relates to a kind of flexibility coat copper plate with mulch film and preparation method thereof.
Background technology
In recent years, the development of information communication industry has driven the manufacturing development of microelectronics, and flexible printed circuit has obtained using widely, and mulch film is to be covered on after the flexible circuitry moulding, and circuit is played protection.Polyimide is one of thermotolerance macromolecular material; Have characteristics such as high thermal stability, high-wearing feature, excellent electric insulating quality and resist chemical, radiation hardness, often be widely used in high-tech areas such as aircraft, automobile, semi-conductor and photovaltaic material, the polyimide mulch film of using like copper-clad plate; It is generally the sizing agent of Kapton collocation different thickness; Be combined into the compound polyimide mulch film of variable thickness after the curing, yet because compound complex structure, its mulch film is because of sizing agent kind and curing factor; The surface is easy to occur all performances of defective, weathering resistancies etc. such as bad order such as flake, pit and poor heat resistance has very big deficiency; And simultaneously, modern society's source radiation is more and more, like solar infrared, ultraviolet ray, computer radiate, cellular radiation, factory floor radiation ... Too much radiation; Cause that human body is dizzy, headache, tired, have a sleepless night or have nightmares, hypomnesis, depressed; Even immunological competence decline, being easy to regard to bacteria infection, this just exists certain weak point.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art, provides a kind of and has higher thermotolerance, flame retardancy, electrical apparatus insulation performance, good appearance and the radiation-resistant flexibility coat copper plate of ability with mulch film and preparation method thereof.
A kind of flexibility coat copper plate of the present invention with the technical scheme that mulch film adopted is: by weight, it is composed of the following components:
30～40 parts of solvent epoxy varnishs
10～20 parts of solvent-borne type epoxy toughening agent
6～25 parts of halogen-free flame retardantss
1～3 part of antiradiation agent
1～3 part of additive
20～40 parts of solvent I.
Wherein, Said solvent epoxy varnish draws for halogen-free epoxy resin and solvent II are dissolved by mass ratio 100:50～200 fully; Said solvent II preferably adopts acetone solvent or butanone solvent; The agent of said solvent-borne type epoxy toughening draws for epoxy toughening agent and solvent III are dissolved by mass ratio 100:250～700 fully, and said solvent III preferably adopts butanone solvent.
Wherein said halogen-free epoxy resin is with advantages such as its excellent electrical apparatus insulation property, good cementability, thermotolerance and chemicalstabilities and be widely used; Though thermal conductivity is relatively poor; But can remedy through the good mineral filler of thermal conductivity, so we adopt epoxy resin as basic resin of the present invention; In order to guarantee enough film-forming propertiess, need carry out modification in addition, increase its toughness epoxy resin; Therefore need to increase the epoxy toughening agent; For example the mixture of one or more in carboxy nitrile rubber, nbr carboxyl terminal, cardanol, polypropylene glycol diglycidyl ether, the linoleic acid dimer diglycidylether carries out modification to epoxy resin, in addition, also need consider the problem of halogen; So; Said halogen-free epoxy resin is one or more the mixture in bisphenol A-type halogen-free epoxy resin, Bisphenol F type halogen-free epoxy resin, the bisphenol E-type halogen-free epoxy resin, has added antiradiation agent, can play radiation-resistant effect like this.
Further, said halogen-free flame retardants comprises one or more the mixture in the halogen-free flame retardantss such as white lake, Marinco H, silicon-dioxide, phosphoric acid salt, SULPHOSUCCINIC ACID ESTER.
Further, said antiradiation agent is the nano material of copper or zinc element or titanium elements or W elements.
Further; Said additive comprises solidifying agent and promotor; Said solidifying agent does not have particular restriction; Anyly typically can use as the material of epoxy curing agent, the mixture of one or more in polyamines base solidifying agent, anhydride group solidifying agent, resole, the aminoresin for example, above-mentioned polyamines base solidifying agent comprises aliphatic amido solidifying agent such as NSC 446 etc.; Alicyclic amido solidifying agent such as isophorone diamine; The ah aromatic amihe-based solidifying agent, like MDA, diaminodiphenylsulfone(DDS), Dyhard RU 100 etc.Above-mentioned anhydride group solidifying agent comprises Tetra hydro Phthalic anhydride etc.; Said promotor glyoxaline compound is like 2 monomethyl imidazoles ureas, 2-ethyl-4-methylimidazole, imidazole salts complex compound, 2-benzylimidazoline, or is one or more mixture in Resorcinol, dihydroxyphenyl propane, phenol, the meta-cresol.
Further, said solvent I is one or more a mixture such as acetone, butanone, EGME, propylene glycol monomethyl ether, N ' N N, toluene.
The technical scheme that the preparation method adopted of the sizing agent of a kind of stiffening plate of the present invention is: it may further comprise the steps:
Said halogen-free epoxy resin and said solvent II are pressed in mass ratio 100:50 ~ 200 adding containers, be stirred to stirrer and be dissolved into solvent epoxy varnish fully, be recorded as component A;
(b): said toughner and said solvent III are pressed in mass ratio 100:250 ~ 700 adding containers, be stirred to it with stirrer and be dissolved as the agent of solvent-borne type epoxy toughening fully, be recorded as component B;
(c): after more said component A, said B component and said halogen-free flame retardants, said antiradiation agent, said additive, said solvent I being added by suitable mass ratio and stirring, make the halogen epoxy adhesive;
(d): said sizing agent is coated on the Kapton and semicure, be combined into flexibility coat copper plate through excess temperature baking back with separate-type paper then and use mulch film, process finished product through hanging down the excessive glue amount of temperature control then.
The invention has the beneficial effects as follows: because the present invention adopts halogen-free epoxy resin to replace original polyester resin is main resin; Add modes such as soluble halogen-free flame retardants filler, said epoxy toughening agent, other auxiliary agent; The stiffening plate of realizing the preparation of industriallization volume production is non-halogen; And have higher thermotolerance, flame retardancy and electrical apparatus insulation performance simultaneously, and overcome bad order after the multilayer polyimide film is compound etc. preferably, and the adding of an amount of antiradiation agent; Can play radiation-resistant effect, so the present invention has higher thermotolerance, flame retardancy, electrical apparatus insulation performance, good appearance and ability radioprotective.
Embodiment
Embodiment one:
Solvent epoxy varnish 32 weight parts, solvent-borne type epoxy toughening agent 18 weight parts, white lake 10 weight parts, SULPHOSUCCINIC ACID ESTER 3.5 weight parts, zinc element 1.50 weight parts, Dyhard RU 100 1.88 weight parts, 2 monomethyl imidazoles ureas, 0.12 weight part, butanone 33 weight parts; Said solvent epoxy varnish is for drawing for halogen-free epoxy resin and acetone solvent or butanone solvent dissolves by mass ratio 100:50～200 fully, and the agent of solvent-borne type epoxy toughening draws for epoxy toughening agent and butanone solvent are dissolved safely by mass ratio 100:250～700.
Embodiment two:
Solvent epoxy varnish 32 weight parts, solvent-borne type epoxy toughening agent 15 weight parts, white lake 10 weight parts, SULPHOSUCCINIC ACID ESTER 4.5 weight parts, zinc element 1.50 weight parts, Dyhard RU 100 1.88 weight parts, 2 monomethyl imidazoles ureas, 0.12 weight part, butanone 35 weight parts.
Embodiment three:
Solvent epoxy varnish 32 weight parts, solvent-borne type epoxy toughening agent 13 weight parts, white lake 10 weight parts, SULPHOSUCCINIC ACID ESTER 5.5 weight parts, zinc element 1.50 weight parts, Dyhard RU 100 1.88 weight parts, 2 monomethyl imidazoles ureas, 0.12 weight part, butanone 36 weight parts.
Embodiment four:
Solvent epoxy varnish 35 weight parts, solvent-borne type epoxy toughening agent 20 weight parts, white lake 8 weight parts, SULPHOSUCCINIC ACID ESTER 2.7 weight parts, zinc element 1.80 weight parts, Dyhard RU 100 1.41 weight parts, 2 monomethyl imidazoles ureas, 0.09 weight part, butanone 31 weight parts.
Embodiment five:
Solvent epoxy varnish 35 weight parts, solvent-borne type epoxy toughening agent 15 weight parts, white lake 8 weight parts, SULPHOSUCCINIC ACID ESTER 2.7 weight parts, zinc element 1.80 weight parts, Dyhard RU 100 1.41 weight parts, 2 monomethyl imidazoles ureas, 0.09 weight part, butanone 38 weight parts.
Embodiment six:
Solvent epoxy varnish 35 weight parts, solvent-borne type epoxy toughening agent 13 weight parts, white lake 8 weight parts, SULPHOSUCCINIC ACID ESTER 2.7 weight parts, zinc element 1.80 weight parts, Dyhard RU 100 1.41 weight parts, 2 monomethyl imidazoles ureas, 0.09 weight part, butanone 36 weight parts.
Embodiment seven:
Solvent epoxy varnish 37 weight parts, solvent-borne type epoxy toughening agent 15 weight parts, SULPHOSUCCINIC ACID ESTER 10 weight parts, zinc element 2.20 weight parts, Dyhard RU 100 1.69 weight parts, 2 monomethyl imidazoles ureas, 0.11 weight part, butanone 34 weight parts.
Embodiment eight:
Solvent epoxy varnish 37 weight parts, solvent-borne type epoxy toughening agent 13 weight parts, SULPHOSUCCINIC ACID ESTER 10 weight parts, zinc element 2.20 weight parts, Dyhard RU 100 1.69 weight parts, 2 monomethyl imidazoles ureas, 0.11 weight part, butanone 36 weight parts.
Comparative Examples nine:
Vibrin 36 weight parts, solvent-borne type epoxy toughening agent 20 weight parts, Dyhard RU 100 1.69 weight parts, 2 monomethyl imidazoles ureas, 0.09 weight part, butanone 43.5 weight parts.
Above-mentioned nine kinds of mulch films are tested, specifically seen table 1.
Table 1
Can find out that from above table embodiment seven and eight is preferable combination of the present invention, this be because; Selecting for use of fire retardant also is important, and above-mentioned non-soluble halogen-free flame retardants is many more, and thermotolerance is poor more; And when all adopting soluble halogen-free flame retardants, thermotolerance can reach 300 °.
The present invention mainly contains following some advantage 1, adopts halogen epoxy resin, more can satisfy the demand of market to non-halogen material, and is safer to environment; 2, epoxy resin is as main resin; Have very good then performance, insulating property and the hot properties of anti-the soldering iron; More can adapt to the application of FPC aspect heat resistance; Especially under the situation of using the PI base material, even also have superior anti-soldering iron high-temperature behavior and dimensional stability after adding wet treatment; 3, adopt the organic filler of solubility, can overcome the bad order of composite structure preferably; 4, the present invention has good difficulty combustion effect simultaneously in non-halogen, good thermotolerance, and terminal applies is reached difficult combustion grade, and is safer; 5, the copper-clad plate that utilizes this mulch film to process has radiation-resistant performance; 6, low from shape power, be prone to processing, possess splendid excessive glue amount stability, be applicable to fast pressure pressure transmission mode.
The present invention is mainly used in the effect of FPC plate surface coverage insulation protection, also can be used in the surface adhesion insulation of precise electronic handware, like computer, and the insulation of the cell connector of handheld device etc. etc.
Claims (10)
1. a flexibility coat copper plate is used mulch film, and this flexibility coat copper plate is composited by sizing agent and separate-type paper with mulch film, it is characterized in that: by weight, said sizing agent is composed of the following components:
30～40 parts of solvent epoxy varnishs
10～20 parts of solvent-borne type epoxy toughening agent
6～25 parts of halogen-free flame retardantss
1～3 part of antiradiation agent
1～3 part of additive
20～40 parts of solvent I.
2. a kind of flexibility coat copper plate according to claim 1 is used mulch film; It is characterized in that: said solvent epoxy varnish draws for halogen-free epoxy resin and solvent II are dissolved by mass ratio 100:50～200 fully, and the agent of said solvent-borne type epoxy toughening is epoxy toughening agent and solvent III to be dissolved by mass ratio 100:250～700 fully draw.
3. a kind of flexibility coat copper plate according to claim 2 is used mulch film, it is characterized in that: said solvent II is acetone solvent or butanone solvent, and said solvent III is a butanone solvent.
4. a kind of flexibility coat copper plate according to claim 1 is used mulch film, it is characterized in that: said halogen-free epoxy resin is one or more the mixture in bisphenol A-type halogen-free epoxy resin, Bisphenol F type halogen-free epoxy resin, the bisphenol E-type halogen-free epoxy resin.
5. a kind of flexibility coat copper plate according to claim 1 is used mulch film, it is characterized in that: said epoxy toughening agent is one or more the mixture in carboxy nitrile rubber, nbr carboxyl terminal, cardanol, polypropylene glycol diglycidyl ether, the linoleic acid dimer diglycidylether.
6. a kind of flexibility coat copper plate according to claim 1 is used mulch film, it is characterized in that: said antiradiation agent is the nano material of copper or zinc element or titanium elements or W elements.
7. a kind of flexibility coat copper plate according to claim 1 is used mulch film, it is characterized in that: said halogen-free flame retardants comprises one or more the mixture in white lake, Marinco H, silicon-dioxide, phosphoric acid salt, the SULPHOSUCCINIC ACID ESTER.
8. a kind of flexibility coat copper plate according to claim 1 is used mulch film; It is characterized in that: said additive comprises solidifying agent and promotor; Said solidifying agent is one or more the mixture in aromatic polyamine, acid anhydrides, resole, aminoresin, Dyhard RU 100 and the hydrazides, and said promotor is one or more mixture in 2 monomethyl imidazoles ureas, 2-ethyl-4-methylimidazole, imidazole salts complex compound, 2-benzylimidazoline, Resorcinol, dihydroxyphenyl propane, phenol, the meta-cresol.
9. a kind of flexibility coat copper plate according to claim 1 is used mulch film, it is characterized in that: said solvent I is one or more a mixture such as acetone, butanone, EGME, propylene glycol monomethyl ether, N ' N N, toluene.
One kind according to claim 1 flexibility coat copper plate it is characterized in that with the making method of mulch film: it may further comprise the steps:
(a): said halogen-free epoxy resin and said solvent II are pressed in mass ratio 100:50 ~ 200 adding containers, be stirred to stirrer and be dissolved into solvent epoxy varnish fully, be recorded as component A;
(b): said toughner and said solvent III are pressed in mass ratio 100:250 ~ 700 adding containers, be stirred to it with stirrer and be dissolved as the agent of solvent-borne type epoxy toughening fully, be recorded as component B;
(c): after more said component A, said B component and said halogen-free flame retardants, said antiradiation agent, said additive, said solvent I being added by suitable mass ratio and stirring, make the halogen epoxy adhesive;
(d): coat on the Kapton said sizing agent and semicure, after the excess temperature baking, be combined into flexibility coat copper plate then and use mulch film with separate-type paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201210168343XA CN102702989A (en) | 2012-05-28 | 2012-05-28 | Cover film for flexible copper clad plate and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210168343XA CN102702989A (en) | 2012-05-28 | 2012-05-28 | Cover film for flexible copper clad plate and preparation method thereof |
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Cited By (6)
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| CN102984886A (en) * | 2012-11-16 | 2013-03-20 | 欣兴同泰科技（昆山）有限公司 | Two-sided flexible printed circuit (FPC) roll-type material-receiving production process |
| CN106398590A (en) * | 2016-09-13 | 2017-02-15 | 深圳市海纳泰兴电子有限公司 | Halogen-free cover film adhesion agent |
| CN106675454A (en) * | 2016-12-31 | 2017-05-17 | 铜陵华科电子材料有限公司 | Solvent material formula applied to high-CTI-value and CAF-resistant copper-clad plates |
| CN110511707A (en) * | 2019-08-08 | 2019-11-29 | 西安航天三沃化学有限公司 | A kind of epoxy adhesive and apply and methods for using them |
| CN110746897A (en) * | 2019-09-23 | 2020-02-04 | 深圳清大中康科技有限公司 | Flexible material suitable for environment-friendly manufacture procedure flexible circuit board and production process |
| CN115926576A (en) * | 2022-12-13 | 2023-04-07 | 东莞市毅联电子科技有限公司 | Shading coating for flexible circuit board and preparation method and use method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102984886A (en) * | 2012-11-16 | 2013-03-20 | 欣兴同泰科技（昆山）有限公司 | Two-sided flexible printed circuit (FPC) roll-type material-receiving production process |
| CN102984886B (en) * | 2012-11-16 | 2016-02-10 | 欣兴同泰科技（昆山）有限公司 | Two-sided FPC rolling splicing production technology |
| CN106398590A (en) * | 2016-09-13 | 2017-02-15 | 深圳市海纳泰兴电子有限公司 | Halogen-free cover film adhesion agent |
| CN106675454A (en) * | 2016-12-31 | 2017-05-17 | 铜陵华科电子材料有限公司 | Solvent material formula applied to high-CTI-value and CAF-resistant copper-clad plates |
| CN110511707A (en) * | 2019-08-08 | 2019-11-29 | 西安航天三沃化学有限公司 | A kind of epoxy adhesive and apply and methods for using them |
| CN110746897A (en) * | 2019-09-23 | 2020-02-04 | 深圳清大中康科技有限公司 | Flexible material suitable for environment-friendly manufacture procedure flexible circuit board and production process |
| CN115926576A (en) * | 2022-12-13 | 2023-04-07 | 东莞市毅联电子科技有限公司 | Shading coating for flexible circuit board and preparation method and use method thereof |
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Application publication date: 20121003 |