CN102181238B - Heat-cured high-intensity flaky adhesive for automobile and preparation method thereof - Google Patents
Heat-cured high-intensity flaky adhesive for automobile and preparation method thereof Download PDFInfo
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- CN102181238B CN102181238B CN 201110098117 CN201110098117A CN102181238B CN 102181238 B CN102181238 B CN 102181238B CN 201110098117 CN201110098117 CN 201110098117 CN 201110098117 A CN201110098117 A CN 201110098117A CN 102181238 B CN102181238 B CN 102181238B
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Abstract
The invention provides a heat-cured high-intensity flaky adhesive for an automobile and a preparation method thereof. The heat-cured high-intensity flaky adhesive for the automobile comprises three layers, wherein the upper layer is made of glass fiber cloth, the middle layer is made of a high-intensity adhesive, and the bottom layer is made of barrier paper. The high-intensity adhesive is prepared from synthetic rubber, a plasticizer, epoxy resin, thermoplastic resin, tackifying resin, a curing agent, a vulcanizing agent, an accelerating agent, an anti-aging agent and calcium carbonate. Due to the adoption of the flaky adhesive, the rigidity of a metal sheet can be increased greatly in the automobile manufacturing process, the running noise of the automobile can be reduced, and the comfort and the safety of the automobile are ensured. The heat-cured high-intensity flaky adhesive has high adhesion to an oil surface metal material, can be operated manually and directly in the construction process, is non-sticky, nontoxic and tasteless, has high manufacturability, is prevented from moving, and is convenient to use. The flaky adhesive can be cut according to different requirements on positions, sizes and shapes and can be stored for over 3 months at the temperature of 25 DEG C.
Description
Technical field
The present invention relates to adhesive material, particularly a kind of automobile thermofixation high-strength sheet glue and preparation method thereof.
Background technology
In order to save the energy, automobile is wanted lightweight, one of its method is to reduce the thickness made from steel plate, but steel plate attenuation meeting descends body stiffness, especially positions such as inner plate of car door, door handle, bonnet inboard, roof, wheel cover, gusset easily produce noise and resonance under steam, when meeting accident collision, impact energy absorbs and diminishes, and injures the occupant easily.Make the automobile lightweight, do not reduce the rigidity of vehicle body again, to guarantee occupant safety, need a kind of low-gravity high-strength sheet glue of research and development, make it to be used for applying with vehicle body stress raiser steel plate, to improve flexural strength, rigidity, the shock resistance of steel plate, promote the safety performance of vehicle.
Summary of the invention
The objective of the invention is in order to solve in automobile making because the problems referred to above that the steel plate attenuation exists, provide a kind of nontoxic, tasteless, pollution-free and have good pasta cementability especially, the automobile that can increase steel sheet rigidity is with thermofixation high-strength sheet glue and preparation method thereof.
This sheet glue is made of 3-layer composite material, and the superiors are the glass fibre cloth material, and the centre is a high strength glue, and bottom is an interleaving paper, and this matrix material can be made various geometrical dimensions and shape as required.This thermofixation high-strength sheet glue also has good manual operations when guaranteeing enough bonding strengths and good vibration silencer.Can be according to particular location size and Special Circumstances, throw off the molding film interleaving paper with hand after, film is placed on required place compacting, floating.
Technical scheme of the present invention is: a kind of automobile thermofixation high-strength sheet glue, it is characterized in that: described sheet glue comprises three layers, the upper strata is a glasscloth, the centre is a high strength glue, bottom is an interleaving paper, described high strength glue is the composition of forming by weight percentage, and its component is formed and comprised: synthetic rubber 20~30%; Softening agent 10~15%; Resins, epoxy 20~30%; Thermoplastic resin 5~10%; Tackifying resin 3~6%; Solidifying agent 1~5%; Vulcanizing agent 1~6%; Promotor 1~2%; Anti-aging agent 0.1~2%; Strengthening agent 3~10%; Lime carbonate 20~30%.
A kind of automobile preparation method of thermofixation high-strength sheet glue, it is characterized in that: may further comprise the steps: a. according to formula rate the use for synthetic rubber mill is plasticated and mixing back and softening agent, Resins, epoxy,, 50% lime carbonate of tackifying resin, anti-aging agent, strengthening agent and formula rate mixes, at rotating ratio be to make even paste on the three-roller of 1:3:9; B. according to formula rate with 50% lime carbonate of thermoplastic resin, solidifying agent, vulcanizing agent, promotor and formula rate with make even paste and mix, on the three-roller of rotating ratio 1:2:4, make soft decorating film; C. extrude by dimensional requirement with forcing machine, be high strength glue; D. on high strength glue deposited unification layer glasscloth, below high strength glue deposited unification layer interleaving paper, press the dimensional requirement severing at last.
The invention has the beneficial effects as follows: adopt the present invention, can make metal sheet big area enhancing rigidity in the automobile making process, can reduce the noise in the automobilism, guarantee the comfortable safety of automobile.This thermofixation high-strength sheet glue and pasta metallic substance adhesion property are good, and in the construction process, direct control is tack-free, nontoxic, tasteless by hand, and good manufacturability, and is unshift, easy to use.Can be according to different sites, the cutting of different size shape need, 25 ℃ of following storage periods greater than 3 months.
Embodiment
The invention will be further described below in conjunction with embodiment: automobile comprises three layers with thermofixation high-strength sheet glue, the upper strata is a glasscloth, the centre is a high strength glue, bottom is an interleaving paper, and the synthetic rubber in the high strength glue of middle layer is selected any one or two kinds in the paracril, liquid acrylonitrile butadiene rubber, carboxyl end of the liquid acrylonitrile-butadiene rubber of acrylonitrile content 31~35%, mooney viscosity 50~60 for use.
Softening agent in the high strength glue is selected any one or two kinds in dibutyl phthalate, dioctyl phthalate (DOP), Octyl adipate, the dioctyl sebacate for use.
It is any one or two kinds among the phenolic aldehyde epoxy F51 of the bisphenol A diglycidyl ether E51 of 0.48~0.54mol/100g, bisphenol A diglycidyl ether E44 that oxirane value is 0.41~0.47mol/100g, oxirane value 〉=0.5 that Resins, epoxy in the high strength glue is selected oxirane value for use.
It is that 2000~3000 pvc resin paste grade P440, vinyl acetate content are any one in 5% the vinyl chloride-vinyl acetate interpolymer paste resin that thermoplastic resin in the high strength glue is selected molecular weight for use.
It is 80~100 ℃ terpine resin that tackifying resin in the high strength glue is selected softening temperature for use, in the petroleum resin any one.
Solidifying agent in the high strength glue is selected any one in Dyhard RU 100, the sebacic dihydrazide for use.
Vulcanizing agent choice of powder shape sulphur in the high strength glue.
Promotor in the high strength glue is selected captax (2-mercaptobenzothiazole), altax (dibenzothiazyl disulfide), TM monex TD(tetramethyl-thiuram disulfide for use), any one or two kinds in the accelerant CZ (N cyclohexyl 2 benzothiazole sulfenamide).
Anti-aging agent in the high strength glue is selected anti-aging agent RD (2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer), anti-aging agent 246(2,4,6-tri-butyl-phenol for use) in any one.
Strengthening agent in the high strength glue is selected any one in oven process carbon black, the channel black for use.
Lime carbonate in the high strength glue is selected for use with stearic acid and is carried out surface-treated SPT nano-calcium carbonate.
Embodiment 1(high strength glue compositions in weight percentage): 20% paracril; 11% dioctyl phthalate (DOP); 25% bisphenol A diglycidyl ether E51; 10% pvc resin paste grade P440; 4.5% terpine resin; 3.3% Dyhard RU 100; 2 % sulphur; 0.6% altax; 0.3% TM monex TD; 0.1% anti-aging agent RD; 3.0% oven process carbon black; The 20.2%SPT nano-calcium carbonate.
Paracril in the foregoing description 1 plasticated with mill and mixing after, 50%SPT nano-calcium carbonate according to proportioning and dioctyl phthalate (DOP), bisphenol A diglycidyl ether E51, terpine resin, anti-aging agent RD, oven process carbon black and proportioning mixes, and at rotating ratio is to make even paste on the three-roller of 1:3:9; With the 50%SPT nano-calcium carbonate of the pvc resin paste grade in the foregoing description 1, Dyhard RU 100, sulphur, altax, TM monex TD and proportioning with make even paste and mix, on the three-roller of rotating ratio 1:2:4, make soft decorating film and obtain the finished product material; Extrude film at the moulding forcing machine again, be high strength glue; Simultaneously apply glasscloth at the high strength film, another side applies interleaving paper, and the film of determining qualified size with sanction glue machine promptly obtains finished product.
Embodiment 2(high strength glue compositions in weight percentage): 15% paracril; 10% liquid acrylonitrile butadiene rubber; 8% dibutyl phthalate; 2% Octyl adipate; 22% bisphenol A diglycidyl ether E44; 6% vinyl chloride-vinyl acetate interpolymer paste resin; 3.5% petroleum resin; 1.0% Dyhard RU 100; 2.0% sulphur; 1.2% captax; 0.3% anti-aging agent 246; 3.2% channel black; 25.8% SPT nano-calcium carbonate.
Paracril in the foregoing description 2 plasticated with mill and mixing after, 50%SPT nano-calcium carbonate according to proportioning and liquid acrylonitrile butadiene rubber, dibutyl phthalate, Octyl adipate, bisphenol A diglycidyl ether E44, petroleum resin, anti-aging agent 246, channel black and proportioning mixes, and at rotating ratio is to make even paste on the three-roller of 1:3:9; With the 50%SPT nano-calcium carbonate of vinyl chloride-vinyl acetate interpolymer paste resin, Dyhard RU 100, sulphur, captax and proportioning in the foregoing description 2 with make even paste and mix, on the three-roller of rotating ratio 1:2:4, make soft decorating film and obtain the finished product material; Extrude film at the moulding forcing machine again, be high strength glue; Simultaneously apply glasscloth at the high strength film, another side applies interleaving paper, and the film of determining qualified size with sanction glue machine promptly obtains finished product.
Embodiment 3(high strength glue compositions in weight percentage): 11% paracril; 11% carboxyl end of the liquid acrylonitrile-butadiene rubber; 5% dioctyl phthalate (DOP); 5% dioctyl sebacate; 11.5% bisphenol A diglycidyl ether E51; 10.5% phenolic aldehyde epoxy F51; 6% pvc resin paste grade P440; 3.8% terpine resin; 1.0% sebacic dihydrazide; 2.5% sulphur; 1.3% accelerant CZ; 0.5% anti-aging agent RD; 3.5% oven process carbon black; 27.4% SPT nano-calcium carbonate.
Paracril in the foregoing description 3 plasticated with mill and mixing after, 50%SPT nano-calcium carbonate according to proportioning and carboxyl end of the liquid acrylonitrile-butadiene rubber, dioctyl phthalate (DOP), dioctyl sebacate, bisphenol A diglycidyl ether E51, phenolic aldehyde epoxy F51, terpine resin, anti-aging agent RD, oven process carbon black and proportioning mixes, and at rotating ratio is to make even paste on the three-roller of 1:3:9; With the 50%SPT nano-calcium carbonate of the pvc resin paste grade in the foregoing description 3, sebacic dihydrazide, sulphur, accelerant CZ and proportioning with make even paste and mix, on the three-roller of rotating ratio 1:2:4, make soft decorating film and obtain the finished product material; Extrude film at the moulding forcing machine again, be high strength glue; Simultaneously apply glasscloth at the high strength film, another side applies interleaving paper, and the film of determining qualified size with sanction glue machine promptly obtains finished product.
Above finished product heats 30~60min and solidifies under 140~170 ℃ of conditions, record technical indicator and be: outward appearance (range estimation): black sheet, non-cracking, fold, layering; The interleaving paper separability: interleaving paper is peelable, does not have cull after the strip off on the interleaving paper; Initial bonding force (N/25mm): 15; Density (g/cm
3): 1.32; Non-volatile content (%): 98.5; Flexural strength (N): 2mm displacement: 102, maximum value: 310.
Claims (2)
1. an automobile is with thermofixation high-strength sheet glue, and it is characterized in that: described sheet glue comprises three layers, and the upper strata is a glasscloth, the centre is a high strength glue, bottom is an interleaving paper, and described high strength glue is the composition of forming by weight percentage, and its component is formed and comprised:
Liquid acrylonitrile butadiene rubber 20~30%
Dibutyl phthalate 10~15%
Resins, epoxy 20~30%
Vinyl chloride-vinyl acetate interpolymer paste resin 5~10%
Terpine resin 3~6%
Dyhard RU 100 1~5%
Powdered sulphur 1~6%
Promotor 1~2%
Anti-aging agent RD 0.1~2%
Strengthening agent 3~10%
Nano-calcium carbonate 20~30%;
Vinyl acetate content is 5% in the vinyl chloride-vinyl acetate interpolymer paste resin wherein; Promotor is selected any one or two kinds in captax, altax, TM monex TD, the accelerant CZ for use; Strengthening agent is selected any one in oven process carbon black, the channel black for use.
2. automobile as claimed in claim 1 is characterized in that with thermofixation high-strength sheet glue: the Resins, epoxy in the high strength glue is selected any one or two kinds among bisphenol A diglycidyl ether E51, bisphenol A diglycidyl ether E44, the phenolic aldehyde epoxy F51 for use.
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JP6215005B2 (en) * | 2013-11-08 | 2017-10-18 | 東洋ゴム工業株式会社 | Method for producing rubber composition |
CN104449506B (en) * | 2014-11-25 | 2017-02-22 | 三友(天津)高分子技术有限公司 | Sing-component epoxy resin adhesive capable of quickly curing at 80 DEG C |
CN106143341B (en) * | 2015-04-17 | 2018-09-07 | 故城县衡岳汽车刹车总成附件厂 | Novel damping noise reduction plank and its production technology |
EP3383966A4 (en) * | 2015-12-01 | 2019-07-03 | 3M Innovative Properties Company | B-stageable adhesive composition |
CN105542695A (en) * | 2016-02-02 | 2016-05-04 | 江苏同盟汽车零部件实业有限公司 | High-damping reinforcing rubber sheet and preparation method thereof |
CN105925212A (en) * | 2016-05-19 | 2016-09-07 | 太仓善融信息服务有限公司 | Green latex rubber adhesive |
CN105950063A (en) * | 2016-05-19 | 2016-09-21 | 太仓善融信息服务有限公司 | Preparation method of green latex type rubber based adhesive |
CN106085294B (en) * | 2016-07-19 | 2018-06-12 | 柳州市兴拓工贸有限责任公司 | Automobile multifunctional damping film and preparation method thereof |
CN107083223A (en) * | 2017-06-06 | 2017-08-22 | 三友(天津)高分子技术有限公司 | A kind of inorganic whisker modified damping noise reduction film |
CN107177338A (en) * | 2017-06-06 | 2017-09-19 | 三友(天津)高分子技术有限公司 | A kind of High Damping Performance film |
CN107556927A (en) * | 2017-08-01 | 2018-01-09 | 常州彤骉贸易有限公司 | A kind of reinforced rubber sheet |
US10865326B2 (en) | 2017-09-20 | 2020-12-15 | Ppg Industries Ohio, Inc. | Coating compositions, elastic barrier coatings formed therefrom, and methods of applying such coatings |
US10836924B2 (en) | 2019-03-15 | 2020-11-17 | Ppg Industries Ohio, Inc. | Coating compositions and elastic barrier coatings formed therefrom |
US10829664B2 (en) | 2019-03-15 | 2020-11-10 | Ppg Industries Ohio, Inc. | Coating compositions containing polythioethers and elastic barrier coatings formed therefrom |
CN115216230A (en) * | 2022-07-28 | 2022-10-21 | 天津时利和新材料技术有限公司 | Self-adhesive structural adhesive tape and preparation method thereof |
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US20070293603A1 (en) * | 2006-06-19 | 2007-12-20 | Ashland Licensing And Intellectual Property Llc | Epoxy adhesive composition and use thereof |
CN101497768B (en) * | 2009-03-04 | 2011-08-31 | 三友(天津)高分子技术有限公司 | Silencing film for automobile |
CN102010680B (en) * | 2010-10-28 | 2012-06-27 | 北京龙苑伟业新材料有限公司 | Thermosetting type seam tape composition for seam sealing, seam tape and preparation method of seam tape |
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