CN101906280B - Halogen-free epoxy adhesive for polyethylene terephthalate (PET) protective film or insulation layer and preparation method thereof - Google Patents
Halogen-free epoxy adhesive for polyethylene terephthalate (PET) protective film or insulation layer and preparation method thereof Download PDFInfo
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- CN101906280B CN101906280B CN 201010238334 CN201010238334A CN101906280B CN 101906280 B CN101906280 B CN 101906280B CN 201010238334 CN201010238334 CN 201010238334 CN 201010238334 A CN201010238334 A CN 201010238334A CN 101906280 B CN101906280 B CN 101906280B
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Abstract
The invention discloses a halogen-free epoxy adhesive for a PET protective film or an insulation layer, which is prepared from the following raw materials in part by mass: halogen-free epoxy resin of 30 to 50, solvent of 20 to 60, flexibilizer of 20 to 35, flame retardant of 10 to 30, curing agent of 1 to 5 and promoter of 0.01 to 0.1. A preparation method of the halogen-free epoxy adhesive comprises the following steps of: adding the halogen-free epoxy resin and the solvent into a container according to a mass ratio of 100: 50, stirring till the mixed materials are dissolved completely and recoding the obtained product as a component A; adding the flexibilizer and the solvent into the container according to a mass ratio of 100: 100, stirring till the mixed materials are dissolved completely and recoding the obtained product as a component B; and mixing the component A, the component B, the flame retardant, the curing agent and the promoter according to a mass ratio of (45-60): (40-70): (10-30): (1-5): (0.01-0.1) and uniformly stirring the mixture to obtain the halogen-free epoxy adhesive. Tests show that the halogen-free epoxy adhesive has the heat-resistance temperature of 288 DEG C and the flame-resistance grade of UL94VTM-0 and meets the application requirements of flexible printed circuit (FPC) and flexible flat cable (FFC) terminals on heat resistance, insulation and flame resistance.
Description
Technical field
The present invention relates to the halogen epoxy adhesive of a kind of PET of being applicable to protective membrane or insulation layer, relevant with composition of raw materials and the preparation method of this halogen epoxy adhesive.
Background technology
In prior art, FPC flexible PCB or FFC flexible flat cable are with PET (polyethylene terephthalate) protective membrane or insulation layer tackiness agent matrix resin used, generally with the preparation of halogen epoxy resin or polyester resin is arranged.Fire-retardant owing to there being halogen epoxy resin to adopt halogen element in resin to carry out, so can not satisfy non-halogen requirement.Polyester resin mainly divides in addition halogen and Halogen, and latter's flame retardant properties is relatively poor or not fire-retardant, therefore generally adopt the former, is that to adopt halogen element in resin to carry out fire-retardant equally but the halogen polyester resin is arranged, so can not satisfy non-halogen requirement.Simultaneously, poor because of the polyester resin resistance toheat, be subjected to after temperature yieldingly, even also easy softening transform at a lower temperature, and firing resistance is poor, is difficult to satisfy the application demand of FPC, FFC terminal heatproof.
Therefore, the inventor studies at this point, develops the halogen epoxy adhesive of a kind of PET of being applicable to protective membrane or insulation layer, and to satisfy the application demand of FPC, FFC terminal heatproof, this case produces thus.
Summary of the invention
The purpose of invention is to provide halogen epoxy adhesive and the preparation method of a kind of PET of being applicable to protective membrane or insulation layer, to satisfy the application demand of FPC, FFC terminal heatproof.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of halogen epoxy adhesive that is applicable to PET protective membrane or insulation layer, made in mass ratio by following raw material:
Halogen-free epoxy resin 30～50,
Solvent 20～60,
Toughner 20～35,
Fire retardant 10～30,
Solidifying agent 1～5,
Promotor 0.01～1.
Wherein, the epoxy equivalent (weight) EEW=180 of described halogen-free epoxy resin～850, the mixture of one or more in halogen-free epoxy resin employing bisphenol A-type halogen-free epoxy resin, Bisphenol F type halogen-free epoxy resin, novolac epoxy and other Halogen modified epoxy, as adopt ACE (dicyclopentadiene type), halogen-free epoxy resin can make product structure strengthen, and thermotolerance improves.
Described solvent adopts one or more the mixture such as acetone, butanone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, N ' N dimethyl formamide, as adopting methylethylketone MEK.Solvent is the thickness for when coating controlling diaphragm.
Described toughner adopts paracril or carboxy nitrile rubber, and the mixture of one or more in GPC (gel permeation chromatography technology) molecular weight Mw=5000～1000000 wherein is such as adopting the CTBN paracril.
The mixture of one or more in described fire retardant employing aluminium hydroxide, phosphoric acid salt, phosphoric acid ester and Organophosphorous compounds is as adopting phosphorus flame retardant FAR-03.
Described solidifying agent and promotor are additive, play resin solidification crosslinked action and screening effect.Wherein solidifying agent adopts aromatic amine, anhydrous acids solidifying agent; The mixture of one or more of promotor employing imidazoles, tertiary ammonium salt and other modification promotor.
A kind of preparation method who is applicable to the halogen epoxy adhesive of PET protective membrane or insulation layer the steps include:
The first step adds halogen-free epoxy resin and solvent in container in mass ratio at 100: 50, is stirred to dissolving fully with stirrer, is recorded as the A component;
Second step adds toughner and solvent in container in mass ratio at 100: 100, is stirred to it with stirrer and dissolves fully, is recorded as the B component;
The 3rd step, with above A component: B component: fire retardant: solidifying agent: promotor is (45～60) in mass ratio: (40～70): (10～30): (1～5): add (0.01～0.1), after stirring, make halogen epoxy adhesive of the present invention.
After adopting such scheme; the present invention is because adopt halogen-free epoxy resin; add halogen-free flame retardants, toughner, additive etc.; so; protective membrane or the insulation layer that can realize the preparation of industrialization volume production are non-halogen; reach non-halogen demand; made halogen epoxy adhesive has higher thermotolerance, flame retardancy and electrical apparatus insulation performance; heat resisting temperature reaches 288 ℃ after tested; anti-combustion grade is the UL94VTM-0 level; overcome the defective that polyester adhesive exists, satisfied the application demand of FPC, FFC terminal heat resistance.Tackiness agent of the present invention can adopt accurate coating apparatus making to be applied to protective membrane or the insulation layer of the PET material of FPC, FFC field use.
Embodiment
A kind of halogen epoxy adhesive that is applicable to PET protective membrane or insulation layer that the present invention discloses is to be made in mass ratio by following raw material:
Halogen-free epoxy resin 30～50,
Solvent 20～60,
Toughner 20～35,
Fire retardant 10～30,
Solidifying agent 1～5,
Promotor 0.01～1.
The below provides 8 embodiment, wherein, halogen-free epoxy resin adopts ACE, and solvent adopts MEK, and toughner adopts paracril, fire retardant adopts phosphorus flame retardant FAR-03, solidifying agent adopts aromatic amine type solidifying agent HD-S, and promotor is adopted imidazole type C-11, first adds in container at 100: 50 halogen-free epoxy resin and solvent in mass ratio, be stirred to dissolving fully with stirrer, be recorded as the A component; And toughner and solvent are added in container in mass ratio at 100: 100, be stirred to it with stirrer and dissolve fully, be recorded as the B component; Again with the A component: B component: fire retardant: solidifying agent, promotor: solvent is (45～60) in mass ratio: (40～70): (10～30): (1～5): add (0.01～0.1), after stirring, make the halogen epoxy adhesive, and resistance toheat and anti-combustion grade are tested, be listed as follows:
Halogen epoxy resin is adopted in evidence, the present invention, more can satisfying the market to the demand of non-halogen material, safer to environment; Epoxy resin has more resistance toheat as main resin than vibrin, more can adapt to FPC, the FFC application aspect heat resistance; The present invention has good difficult fuel efficiency fruit simultaneously in non-halogen, good thermotolerance, and terminal applies is reached Fire retardant grade, and is safer.
Claims (1)
- , a kind of halogen epoxy adhesive that is applicable to PET protective membrane or insulation layer, it is characterized in that: made in mass ratio by following raw material:ACE halogen-free epoxy resin 30～37,Methyl ethyl ketone solvent 36,Paracril toughner 20,Phosphorus flame retardant 10.2～22,Aromatic amine curing agent l.41～1.88,Imidazoles promotor 0.09～0.12,The mixture of one or more in described phosphorus flame retardant employing phosphoric acid salt, phosphoric acid ester and Organophosphorous compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010238334 CN101906280B (en) | 2010-07-27 | 2010-07-27 | Halogen-free epoxy adhesive for polyethylene terephthalate (PET) protective film or insulation layer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010238334 CN101906280B (en) | 2010-07-27 | 2010-07-27 | Halogen-free epoxy adhesive for polyethylene terephthalate (PET) protective film or insulation layer and preparation method thereof |
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| Publication Number | Publication Date |
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| CN101906280A CN101906280A (en) | 2010-12-08 |
| CN101906280B true CN101906280B (en) | 2013-05-08 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516914A (en) * | 2011-11-21 | 2012-06-27 | 烟台德邦电子材料有限公司 | Halogen-free flame-retardant epoxy resin electronic pouring sealant |
| CN102660875B (en) * | 2012-05-22 | 2016-06-15 | 厦门市豪尔新材料股份有限公司 | A kind of carbon fiber processing polymeric membrane |
| CN102703011A (en) * | 2012-05-28 | 2012-10-03 | 珠海亚泰电子科技有限公司 | Adhesive of reinforcement plate, and manufacturing method of adhesive |
| CN102689463A (en) * | 2012-05-28 | 2012-09-26 | 珠海亚泰电子科技有限公司 | Flexible copper-clad plate |
| CN102702989A (en) * | 2012-05-28 | 2012-10-03 | 珠海亚泰电子科技有限公司 | Cover film for flexible copper clad plate and preparation method thereof |
| CN104449509B (en) * | 2014-11-28 | 2016-11-30 | 中国航空工业集团公司金城南京机电液压工程研究中心 | A kind of high temperature resistant bonded adhesives |
| CN113619234A (en) * | 2021-07-28 | 2021-11-09 | 山东滨芯电子科技有限公司 | Novel flexible copper-clad substrate material applied to high-frequency and high-speed transmission of 5G communication |
| CN114940773B (en) * | 2022-06-21 | 2023-05-30 | 拓迪化学(上海)有限公司 | PET/epoxy resin ultrathin composite film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005017352A (en) * | 2003-06-23 | 2005-01-20 | Fuji Photo Film Co Ltd | Platemaking method of flexographic printing plate |
| CN102558505A (en) * | 2006-09-29 | 2012-07-11 | 日立化成工业株式会社 | Thermosetting resin composition and prepreg and laminate obtained with the same |
| CN101570620A (en) * | 2008-05-03 | 2009-11-04 | 新高电子材料（中山）有限公司 | Halogen-free flame retardant epoxide resin composition |
| CN101633770B (en) * | 2009-08-28 | 2011-07-20 | 番禺南沙殷田化工有限公司 | Halogen-free flame retardant epoxy resin composite and flexible copper clad laminate prepared with same |
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Effective date of registration: 20200427 Address after: 214028 No.26, Xiqin Road, Xinwu District, Wuxi City, Jiangsu Province Patentee after: WUXI GRACE ELECTRONIC MATERIAL TECHNOLOGY Co.,Ltd. Address before: 511000, No. 1, Po Po Road, Yun Po Industrial Area, Guangdong, Guangzhou Patentee before: GUANGZHOU GRACE ELECTRONIC INDUSTRY Co.,Ltd. |
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