CN103509506A - Stiffener film substrate composition, stiffener film substrate as well as stiffener film and steel plate composite material - Google Patents
Stiffener film substrate composition, stiffener film substrate as well as stiffener film and steel plate composite material Download PDFInfo
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- CN103509506A CN103509506A CN201210214870.XA CN201210214870A CN103509506A CN 103509506 A CN103509506 A CN 103509506A CN 201210214870 A CN201210214870 A CN 201210214870A CN 103509506 A CN103509506 A CN 103509506A
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- epoxy resin
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 50
- 239000010959 steel Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 239000003351 stiffener Substances 0.000 title abstract description 17
- 239000000758 substrate Substances 0.000 title abstract 7
- 229920001971 elastomer Polymers 0.000 claims abstract description 157
- 239000005060 rubber Substances 0.000 claims abstract description 156
- 239000003822 epoxy resin Substances 0.000 claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 26
- 229920013649 Paracril Polymers 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
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- 239000006229 carbon black Substances 0.000 claims description 13
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- 239000004902 Softening Agent Substances 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 241001441571 Hiodontidae Species 0.000 claims description 4
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 235000010985 glycerol esters of wood rosin Nutrition 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- FNJSWIPFHMKRAT-UHFFFAOYSA-N Monomethyl phthalate Chemical class COC(=O)C1=CC=CC=C1C(O)=O FNJSWIPFHMKRAT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
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- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
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- 229920003002 synthetic resin Polymers 0.000 claims description 2
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 229920000459 Nitrile rubber Polymers 0.000 abstract description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 239000002174 Styrene-butadiene Substances 0.000 description 6
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- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
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- 230000003014 reinforcing effect Effects 0.000 description 3
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
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- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- 238000004134 energy conservation Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
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Abstract
The invention provides a stiffener film substrate composition, a stiffener film substrate, a stiffener film and a steel plate composite material comprising the stiffener film. The stiffener film substrate composition comprises epoxy resin, nitrile rubber, butadiene styrene rubber, a curing agent and a tackifier. The prepared stiffener film substrate has strong bonding force with a vehicle body steel plate, the strength of the cured stiffener film substrate is further improved, meanwhile, the vibration noise of a vehicle body can be reduced, and the NVH (Noise Vibration and Harshness) property of a vehicle can be enhanced.
Description
Technical field
The present invention relates to a kind of reinforced rubber sheet basal body composition, the reinforced rubber sheet basal body of being prepared by said composition, reinforced rubber sheet, and the steel plate composite material that comprises this reinforced rubber sheet.
Background technology
Along with scientific and technological development, improving constantly of automobile quality, automobile is just towards high speed, light weight, energy-conservation and comfortable future development, thereby automobile is also more and more higher to the requirement of NVH performance (noise of automobile (Noise), vibration (Vibration), sound vibration roughness (Harshness)), the development trend of automotive light weight technology changes the structure of body of a motor car at present, as outside plate thin-walled property, structural part cavitation etc., this phenomenon will affect the NVH performance of automobile, and its potential safety hazard will damage occupant.For solve this using reach the object of energy-saving consumption-reducing and conventionally use steel sheet as body material, to alleviate in the method for tare, some drawbacks that cause after vehicle body steel plate thin-walled, in order to guarantee the physical strength of vehicle body, at the local reinforced rubber sheet that uses of vehicle body steel plate, strengthen the impact resistance of vehicle body.
77 pages of " Chinese building material " the 1st phases in 2006, theme as in the report of " New-type sheet reinforced rubber sheet ", a kind of automobilesheet reinforced rubber sheet is disclosed, the base-material of this structural reinforcing member for steel panel is polyvinyl chloride resin, epoxy resin, specialty elastomer etc., is successfully applied on automobile.But add after polyvinyl chloride resin the processing performance of reinforced rubber sheet unstable, curing post-shrinkage ratio is larger, lower with the cohesive force of steel plate, and intensity is also lower.In CN 1865345A, disclose a kind of reinforced rubber sheet basal body composite resin for car, bisphenol A type epoxy resin, acrylonitrile content by molecular weight at 378-1000 form at terminal hydroxy liquid divinyl rubber, nano silicon, nano-calcium carbonate, carbon black, superoxide initiation linking agent, solidifying agent dicyandiamide and the rubber modifier ZX-8 of 2000-10000 at paracril, natural rubber, the molecular weight of 15-50 % by weight.The performance of the reinforced rubber sheet that this reinforced rubber sheet basal body composite resin is made is compared with the reinforced rubber sheet of above-mentioned employing polyvinyl chloride resin certain improvement aspect intensity, but still poor with the cohesive force of steel plate, and its intensity does not reach desirable requirement yet.
Summary of the invention
The present invention is lower in order to solve the cohesive force of the reinforced rubber sheet that exists in prior art and steel plate, and the not high technical problem of intensity after solidifying, provide a kind of energy preparation good with the cohesive force of steel plate, and the reinforced rubber sheet basal body composition of the reinforced rubber sheet that the intensity after solidifying is higher, the reinforced rubber sheet basal body of being prepared by said composition, reinforced rubber sheet, and the steel plate composite material that comprises this reinforced rubber sheet.
First object of the present invention is to provide a kind of reinforced rubber sheet basal body composition, and said composition contains epoxy resin, paracril, styrene-butadiene rubber(SBR), solidifying agent and tackifier.
Second object of the present invention is to provide a kind of reinforced rubber sheet basal body, and this reinforced rubber sheet basal body is to be made through mixing, compressing tablet by above-mentioned reinforced rubber sheet basal body composition.
The 3rd object of the present invention is to provide a kind of reinforced rubber sheet, comprises successively reinforced rubber sheet basal body, enhancement layer, and wherein, this reinforced rubber sheet basal body is above-mentioned reinforced rubber sheet basal body.
The 4th object of the present invention is to provide a kind of steel plate composite material, and this steel plate composite material comprises steel plate, the reinforced rubber sheet being bonded together successively, and described steel plate contacts with the reinforced rubber sheet basal body of reinforced rubber sheet, and wherein, reinforced rubber sheet is above-mentioned reinforced rubber sheet.
The present invention surprisingly finds that the cohesive force of reinforced rubber sheet basal body prepared by reinforced rubber sheet basal body composition of the present invention and vehicle body steel plate is strong, and cured strength also further strengthened, and also can reduce body vibrations noise simultaneously, promote the NVH performance of automobile.Infer that reason may be because tackifier itself have certain viscosity, and tackifier are by the connection of molecular linkage, be combined in the reticulated structure of cross-linking system of rubber and epoxy resin, the molecular structure of tackifier is larger, can increase branched structure and the complicacy of system, when product and steel sticking, the vertical multipotency of side chain enough increases the specific surface area of product and steel plate, thereby and utilize the viscosity self possessing to improve the cohesive force of rubber and epoxy-resin systems; In addition, because the molecular structure of tackifier is larger, when it is attached in rubber and epoxy-resin systems reticulated structure, molecule side chain increases the overlapping of molecular structure more, make product bear very large external force, thereby it stick on the intensity that can increase steel plate on steel plate.
Embodiment
The invention provides a kind of reinforced rubber sheet basal body composition, said composition contains epoxy resin, paracril, styrene-butadiene rubber(SBR), solidifying agent and tackifier, the reinforced rubber sheet basal body of preparation and the cohesive force of vehicle body steel plate are strong, and cured strength also further strengthened, also can reduce body vibrations noise simultaneously, promote the NVH performance of automobile.
Preferably, with respect to the epoxy resin of 100 weight parts, the content of described tackifier is 20-50 weight part, and 25-40 weight part more preferably is further optimized the performance of reinforced rubber sheet.
Preferably, tackifier are selected from oiliness tackifying resin, and its molecular structure is larger, can increase branched structure and the complicacy of system, strengthen the cohesive force of reinforced rubber sheet and steel plate, molecular structure is larger, molecule side chain increases the overlapping of molecular structure more, strengthens the intensity after reinforced rubber sheet solidifies.Preferably tackifier are selected from one or more in amides resin, phenolic resinoid, hydrocarbon resin or rosin based resin.In better situation, tackifier are selected from one or more in tert butyl phenolic resin, octyl phenol urea formaldehyde, ester gum, rosin pentaerythritol resin or hydrocarbon resin.Further preferably tackifier are tert butyl phenolic resin and/or octyl phenol urea formaldehyde, and the composition properties of formation is best.
To other composition in reinforced rubber sheet basal body composition and content, can in relative broad range, select, under preferable case, in reinforced rubber sheet basal body composition of the present invention, epoxy resin with respect to 100 weight parts, the content of described paracril is 20-40 weight part, the content of described styrene-butadiene rubber(SBR) is 15-50 weight part, and the content of described solidifying agent is 6-10 weight part, further optimizes the performance of reinforced rubber sheet.
Preferably, epoxy resin is selected from one or more in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin and chlorination bisphenol A type epoxy resin, the epoxy equivalent (weight) of preferred epoxy is 170-240 g/eq, described epoxy resin is 12000-15000cps the viscosity of 25 ℃, further optimize the adhesivity of reinforced rubber sheet and solidify after mechanical property.Epoxy resin of the present invention is commercially available, and the present invention is restriction not, for example, can for the trade mark, be the bisphenol A type epoxy resin of E-53, E-51.
In reinforced rubber sheet basal body composition of the present invention, solidifying agent the present invention is restriction not, the various solidifying agent that can be known to the skilled person, preferred consolidation agent is high-temperature curing agent, can make epoxy resin solidify at 170-250 ℃, can guarantee under product normal temperature to be the soft flaky material of Pasting, paste at the difform reinforcement position that needs of convenient past automobile, can through the hot setting (170-250 ℃) being welded with Painting Shop again, play the strengthening action to product.In better situation, solidifying agent can be selected from one or more in Dyhard RU 100, mphenylenediamine, p-Xylol amine, diaminodiphenyl oxide or phenyl ether tetracid acid anhydride, and further the median size of preferred consolidation agent is 2-20 μ m.
Described paracril is more important for toughness and the operability of described reinforced rubber sheet basal body.Preferably the Mooney viscosity of paracril is 50-60 Mooney point, further optimizes the processing characteristics of rubber.Preferably the acrylonitrile content in paracril is 30-50 % by weight.Paracril of the present invention is commercially available, and the present invention is restriction not, for example the concrete trade mark can JSR N237, JSR N230S, a kind of in JSR N220S, JSR N215SL, JSR N237H, JSR N240S, preferred JSR N220S.
Described styrene-butadiene rubber(SBR) is more important for the cohesive force of described reinforced rubber sheet basal body and vehicle body steel plate.Preferably the Mooney viscosity of styrene-butadiene rubber(SBR) is 46-60 Mooney point, further optimizes the processing characteristics of rubber.Preferably, the butadiene content in styrene-butadiene rubber(SBR) is 50-70 % by weight.Styrene-butadiene rubber(SBR) of the present invention is commercially available, and the present invention is restriction not, for example the concrete trade mark can SBR 1500, SBR 1502, a kind of in SBR 1503, SBR 1712, SBR 1778, preferably SBR 1502.
Preferably, also contain hollow glass microbead in composition, with respect to the epoxy resin of 100 weight parts, the content of hollow glass microbead is 25-50 weight part.Can further effectively reduce the density of made reinforced rubber sheet basal body, the intensity of increase reinforced rubber sheet basal body with reinforced rubber sheet basal body combination of compositions of the present invention, reinforcing effect is further improved.Preferably the median size of hollow glass microbead is 10-75 μ m, density 0.1-0.3g/cm
3.
Preferably, composition also contains mineral filler, and with respect to the epoxy resin of 100 weight parts, the content of described mineral filler is 80-120 weight part.In better situation, mineral filler is selected from talcum powder, calcium carbonate, clay, one or more in silicon-dioxide, mica powder or polynite, and preferably talc powder, calcium carbonate and silicon-dioxide, the median size of mineral filler is 2-13 μ m.With reinforced rubber sheet basal body combination of compositions of the present invention, further increase the mechanical property of goods and/or reduce costs.
In composition of the present invention, can also optionally add one or more in carbon black, softening agent or linking agent.Wherein carbon black not only can further strengthen the mechanical property of goods, and can regulate the color of product, with respect to the epoxy resin of 100 weight parts, preferably the content of carbon black is 0-5 weight part, in better situation, carbon black is thermally oxidized black, and preferably the median size of carbon black is 3-8 μ m.Softening agent can further impel the plasticizing of styrene-butadiene rubber(SBR) and paracril molecule, make the two better crosslinked, thereby can further improve the intensity of product, epoxy resin with respect to 100 weight parts, the content of preferred plasticizer is 0-20 weight part, preferably, softening agent is selected from one or more in phthalic acid methyl esters class and/or aliphatic dibasic acid ester, in better situation, be specifically as follows dibutyl phthalate (DBP), dimethyl phthalate (DMP), dioctyl phthalate (DOP) (DOP), adipic acid ester etc.Linking agent can further strengthen the crosslinked action between styrene-butadiene rubber(SBR) and paracril, improve the intensity of product, epoxy resin with respect to 100 weight parts, preferably the content of linking agent is 0-2 weight part, preferably linking agent is selected from organo-peroxide, can be dicumyl peroxide (DCP), benzoyl peroxide (BPO), ditertiary butyl peroxide (DTBO) etc. in better situation.Commodity all can be purchased.
In reinforced rubber sheet basal body composition of the present invention, can also add as required some other property-modifying additives, the present invention is restriction not, for example, in order to strengthen intensity and the toughness after reinforced rubber sheet basal body of the present invention solidifies, in described reinforced rubber sheet basal body composition, can contain vulcanizing agent, so that paracril, styrene-butadiene rubber(SBR) occur is crosslinked.In order further to promote the effect of sulfuration can to contain activator in reinforced rubber sheet basal body composition of the present invention.In order to improve dispersiveness and the bounding force of each component in described composition, thereby improve the mechanical property of reinforced rubber sheet basal body of the present invention, in reinforced rubber sheet basal body composition of the present invention, can also contain coupling agent etc.Vulcanizing agent, activator and coupling agent the present invention be restriction not, can select and well known to a person skilled in the art various vulcanizing agents, activator and coupling agent.
The present invention provides a kind of reinforced rubber sheet basal body simultaneously, and wherein, this reinforced rubber sheet basal body is to be made through mixing, compressing tablet by above-mentioned reinforced rubber sheet basal body composition.The thickness of this reinforced rubber sheet basal body can be determined according to the reinforcement demand at reinforcement position, and preferably, reinforced rubber sheet basal body is that thickness is the plates of 1.5-1.9mm.
Preferably, mixingly comprise that by styrene-butadiene rubber(SBR), paracril and tackifier, in 80 ℃-100 ℃, rotating speed is mixing 20-25min under turn/min of 60-150, the rear and mixing 10-15min of epoxy resin, then add the mixing 10-15min of solidifying agent.Further preferred mixing comprising styrene-butadiene rubber(SBR), paracril and tackifier in 80 ℃-100 ℃, rotating speed is mixing 20-25min under turn/min of 60-150, after add the mixing 10-15min of epoxy resin of 30-40wt% part, add again linking agent, remaining epoxy resin, mineral filler, hollow glass microbead, softening agent and carbon black etc., after mixing 20-30min, add solidifying agent, mixing 10-15min.
Mixing can banburying in Banbury mixer.Compressing tablet can be suppressed in flakes on molding apparatus, it can be independent material compressing tablet, prepare reinforced rubber sheet basal body, also can be with compressing tablet together after the clamping of separate-type paper, enhancement layer, prepare reinforced rubber sheet, can also be after the clamping of steel plate, enhancement layer together compressing tablet prepare steel plate composite material, can design according to technique.
The present invention also provides a kind of reinforced rubber sheet, comprises successively reinforced rubber sheet basal body, enhancement layer, and this reinforced rubber sheet basal body is above-mentioned reinforced rubber sheet basal body.Preferably, described reinforced rubber sheet also comprises separate-type paper, and described reinforced rubber sheet comprises separate-type paper, reinforced rubber sheet basal body, enhancement layer successively.Reinforced rubber sheet with separate-type paper is easy to store and shift.Described separate-type paper is well known for the person skilled in the art, commercially available.
The preparation method of reinforced rubber sheet of the present invention can, for the described enhancement layer of fitting on a side surface of reinforced rubber sheet basal body of the present invention, obtain reinforced rubber sheet.Also can be by the reinforced rubber sheet basal body composition compressing tablet together with enhancement layer mixing.Also can be separate-type paper to be clamped together with enhancement layer to the reinforced rubber sheet basal body composition mixing then to put on molding apparatus compacting in flakes.The present invention is restriction not.
The present invention also provides a kind of steel plate composite material, and this steel plate composite material comprises steel plate, reinforced rubber sheet basal body and the enhancement layer being bonded together successively, and described reinforced rubber sheet basal body is above-mentioned reinforced rubber sheet basal body.Wherein, in better situation, the Thickness Ratio of steel plate, reinforced rubber sheet basal body and enhancement layer can be 0.6-1.2:0.5-5:0.05-2.Wherein, described enhancement layer is a kind of in glasscloth, nylon fiber cloth, carbon cloth, synthetic resins non-woven fabrics.Described steel plate can be normally used steel plate in auto industry field.
The preparation method of steel plate composite material of the present invention can be at 5-40 ℃, a side surface that there is no enhancement layer of reinforced rubber sheet obtained above is sticked on steel plate, thereby make described reinforced rubber sheet basal body and enhancement layer jointly stick on steel plate, at 170-250 ℃, heat 20-50min, described reinforced rubber sheet basal body layer is solidified, obtain described steel plate composite material.If while also adhering to separate-type paper on a side surface that there is no enhancement layer of reinforced rubber sheet, before will described reinforced rubber sheet being sticked on steel plate, separate-type paper need be peeled off, and by the reinforced rubber sheet basal body surface adhesion of exposing on steel plate, carry out again above-mentioned solidifying, can obtain steel plate composite material of the present invention.
The present invention is further described the present invention in conjunction with specific embodiments.
Embodiment 1
The reinforced rubber sheet basal body composition of the present embodiment: epoxy equivalent (weight) 170-240 gram/equivalent, bisphenol A epoxide resin (South Asia epoxy resin company limited) 100 weight parts of viscosity (25 ℃) 12000-15000cps, acrylonitrile content is at paracril (Japanese strain formula producer) 30 weight parts of 30-50 % by weight, mooney viscosity 50-60, butadiene content is at styrene-butadiene rubber(SBR) (Jilin Chemical producer) 35 weight parts of 50-70 % by weight, mooney viscosity 46-60, tert butyl phenolic resin (Dong Xin chemical industry producer) 20 weight parts, particle diameter 10-75 μ m, density 0.1-0.3g/cm
3hollow glass microbead 35 weight parts, thermally oxidized black 2 weight parts of particle diameter 3-8 μ m, Dyhard RU 100 8 weight parts of particle diameter 2-20 μ m, DOP10 weight part, the calcium carbonate of particle diameter 2-13 μ m and talcum powder 110 weight parts, dicumyl peroxide 1 weight part.
The reinforced rubber sheet basal body of the present embodiment and the preparation method of reinforced rubber sheet are as follows:
(1) first by styrene-butadiene rubber(SBR), paracril and tackifier are put into Banbury mixer in (80 ± 2) ℃, rotating speed is mixing 20min under (80 ± 2) turn/min, then the mixing 10min of epoxy resin that adds 35wt%, form rubber-resin system, add successively again linking agent, remaining epoxy resin, mineral filler, hollow glass microbead, softening agent, carbon black, after mixing 20min, add solidifying agent, continue mixing 10min, the mixture obtaining is cooled to after 40 ℃, be clamped between commercially available glasscloth and separate-type paper in blocks on rolling press, cut into desired shape specification, obtain stiffener film of automobile sample S1.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare stiffener film of automobile sample S2, different is that reinforced rubber sheet basal body composition tackifier used are octyl phenol urea formaldehyde (Dong Xin chemical industry producer).
Embodiment 3
Adopt the method identical with embodiment 1 to prepare stiffener film of automobile sample S3, different is that reinforced rubber sheet basal body composition tackifier used are ester gum (Ding Tai resin company limited).
Embodiment 4
Adopt the method identical with embodiment 1 to prepare stiffener film of automobile sample S4, the amount of different is reinforced rubber sheet basal body composition tackifier used is 25 weight parts.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare stiffener film of automobile sample S5, the amount of different is reinforced rubber sheet basal body composition tackifier used is 30 weight parts.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare stiffener film of automobile sample S6, the amount of different is reinforced rubber sheet basal body composition tackifier used is 40 weight parts.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare stiffener film of automobile sample DS1, different is that reinforced rubber sheet basal body composition does not contain tert butyl phenolic resin tackifier.
Comparative example 2
The LY-306 type structural reinforcing member for steel panel sample DS2 of Beijing Longyuan Weiye Materials Co., Ltd.
Comparative example 3
Reinforced rubber sheet basal body composition in the embodiment 1 of employing CN1865345A is prepared reinforced rubber sheet sample DS3 according to the method for embodiment 1.
Performance test
According to NISSAN engineering specification (8451 film) testing method, detect respectively reinforced rubber sheet sample S1-S6 that above-described embodiment 1-6 and comparative example 1-3 make and maximum deflection power and the maximum distortion of DS1-DS3, result is as shown in table 1.
Adopt following methods test cohesive force: get the steel plate that specification is 200mm * 25mm, after clean, by specification, be that 350mm * 25mm reinforced rubber sheet is removed after separate-type paper and tiled and be attached on steel plate, the bond area of steel plate and reinforced rubber sheet basal body is 150mm * 25mm, with roller roll-in 5 times back and forth, room temperature is tested after placing 30min, adopts universal testing machine to carry out cohesive force test, and draw speed is 100mm/min.Detect respectively reinforced rubber sheet sample S1-S6 that above-described embodiment 1-6 and comparative example 1-3 make and the cohesive force of DS1-DS3, result is as shown in table 1.
Table 1
| ? | Maximum deflection power (N) | Largest deformation amount (mm) | Cohesive force (N/25mm) |
| S1 | 471.32 | 8.86 | 15.78 |
| S2 | 463.21 | 8.49 | 15.12 |
| S3 | 465.32 | 8.58 | 14.20 |
| S4 | 487.46 | 9.60 | 16.34 |
| S5 | 481.97 | 9.35 | 15.98 |
| S6 | 469.78 | 8.79 | 13.24 |
| DS1 | 435.23 | 7.20 | 8.15 |
| DS2 | 413.58 | 6.20 | 7.52 |
| DS3 | 420.39 | 6.51 | 6.85 |
Reinforced rubber sheet basal body prepared by reinforced rubber sheet basal body composition of the present invention and the cohesive force of vehicle body steel plate are strong, are substantially all more than 13N/25mm, be far longer than the cohesive force that does not add tackifying resin and LY-306 and CN1865345A, by contrast S1, S2, S3 and DS1 can find out, add largest deformation amount and the maximum deflection power of the reinforced rubber sheet after tackifying resin to be all greater than the reinforced rubber sheet that does not add tackifying resin, know thus, add tackifying resin can further strengthen largest deformation amount and the bending force of reinforced rubber sheet, increase the intensity after reinforced rubber sheet solidifies, by contrast S1 and DS2, DS3 can find out, reinforced rubber sheet of the present invention is more much larger than the bending force of LY-306 and CN1865345A and deformation quantity, better effects if, also can reduce body vibrations noise simultaneously, promote the NVH performance of automobile.
Claims (26)
1. a reinforced rubber sheet basal body composition, is characterized in that, said composition contains epoxy resin, paracril, styrene-butadiene rubber(SBR), solidifying agent and tackifier.
2. reinforced rubber sheet basal body composition according to claim 1, is characterized in that, with respect to the epoxy resin of 100 weight parts, the content of described tackifier is 20-50 weight part.
3. reinforced rubber sheet basal body composition according to claim 2, is characterized in that, with respect to the epoxy resin of 100 weight parts, the content of described tackifier is 25-40 weight part.
4. reinforced rubber sheet basal body composition according to claim 1, is characterized in that, described tackifier are selected from oiliness tackifying resin.
5. reinforced rubber sheet basal body composition according to claim 4, is characterized in that, described tackifier are selected from one or more in amides resin, phenolic resinoid, hydrocarbon resin or rosin based resin.
6. reinforced rubber sheet basal body composition according to claim 5, is characterized in that, described tackifier are selected from one or more in tert butyl phenolic resin, octyl phenol urea formaldehyde, ester gum, rosin pentaerythritol resin or hydrocarbon resin.
7. reinforced rubber sheet basal body composition according to claim 6, is characterized in that, described tackifier are tert butyl phenolic resin and/or octyl phenol urea formaldehyde.
8. reinforced rubber sheet basal body composition according to claim 1, it is characterized in that, with respect to the epoxy resin of 100 weight parts, the content of described paracril is 20-40 weight part, the content of described styrene-butadiene rubber(SBR) is 15-50 part, and the content of described solidifying agent is 6-10 weight part.
9. reinforced rubber sheet basal body composition according to claim 1, it is characterized in that, described epoxy resin is selected from one or more in bisphenol A type epoxy resin, bisphenol-s epoxy resin, bisphenol f type epoxy resin and chlorination bisphenol A type epoxy resin, the epoxy equivalent (weight) of described epoxy resin is 170-240 g/eq, and described epoxy resin is 12000-15000cps the viscosity of 25 ℃.
10. reinforced rubber sheet basal body composition according to claim 1, it is characterized in that, described solidifying agent is selected from one or more in Dyhard RU 100, mphenylenediamine, p-Xylol amine, diaminodiphenyl oxide or phenyl ether tetracid acid anhydride, and the median size of described solidifying agent is 2-20 μ m.
11. reinforced rubber sheet basal body compositions according to claim 1, is characterized in that, the Mooney viscosity of described paracril is 50-60 Mooney point, and the acrylonitrile content in described paracril is 30-50 % by weight.
12. reinforced rubber sheet basal body compositions according to claim 1, is characterized in that, the Mooney viscosity of described styrene-butadiene rubber(SBR) is 46-60 Mooney point, and the butadiene content in described styrene-butadiene rubber(SBR) is 50-70 % by weight.
13. reinforced rubber sheet basal body compositions according to claim 1, is characterized in that, described composition also contains hollow glass microbead, and with respect to the epoxy resin of 100 weight parts, the content of described hollow glass microbead is 25-50 weight part.
14. reinforced rubber sheet basal body compositions according to claim 13, is characterized in that, the median size of described hollow glass microbead is 10-75 μ m, density 0.1-0.3g/cm
3.
15. reinforced rubber sheet basal body compositions according to claim 1, is characterized in that, described composition also contains mineral filler, and with respect to the epoxy resin of 100 weight parts, the content of described mineral filler is 80-120 weight part.
16. reinforced rubber sheet basal body compositions according to claim 15, it is characterized in that, described mineral filler is selected from talcum powder, calcium carbonate, clay, one or more in silicon-dioxide, mica powder or polynite, and the median size of described mineral filler is 2-13 μ m.
17. reinforced rubber sheet basal body compositions according to claim 1, is characterized in that, described composition also contains one or more in carbon black, softening agent or linking agent; With respect to the epoxy resin of 100 weight parts, the content of described carbon black is 0-5 weight part; The content of described softening agent is 0-20 weight part; The content of described linking agent is 0-2 weight part.
18. reinforced rubber sheet basal body compositions according to claim 17, is characterized in that, described carbon black is thermally oxidized black, and the median size of described carbon black is 3-8 μ m;
Described softening agent is selected from one or more in phthalic acid methyl esters class and/or aliphatic dibasic acid ester;
Described linking agent is selected from organo-peroxide.
19. 1 kinds of reinforced rubber sheet basal bodies, is characterized in that, this reinforced rubber sheet basal body is that the reinforced rubber sheet basal body composition described in any one makes through mixing, compressing tablet in claim 1-18.
20. reinforced rubber sheet basal bodies according to claim 19, it is characterized in that, described mixing comprising styrene-butadiene rubber(SBR), paracril and tackifier in 80 ℃-100 ℃, rotating speed is mixing 20-25min under turn/min of 60-150, afterwards with the mixing 10-15min of epoxy resin, then add the mixing 10-15min of solidifying agent.
21. reinforced rubber sheet basal bodies according to claim 20, it is characterized in that, described mixing comprising styrene-butadiene rubber(SBR), paracril and tackifier in 80 ℃-100 ℃, rotating speed is mixing 20-25min under turn/min of 60-150, after add the mixing 10-15min of epoxy resin of 30-40wt% part, then add linking agent, remaining epoxy resin, mineral filler, hollow glass microbead, softening agent and carbon black, after mixing 20-30min, add solidifying agent, mixing 10-15min.
22. reinforced rubber sheet basal bodies according to claim 19, wherein, this reinforced rubber sheet basal body is that thickness is the plates of 1.5-1.9mm.
23. 1 kinds of reinforced rubber sheets, is characterized in that, comprise successively reinforced rubber sheet basal body, enhancement layer, and this reinforced rubber sheet basal body is the reinforced rubber sheet basal body described in any one in claim 19-22.
24. reinforced rubber sheets according to claim 23, is characterized in that, described reinforced rubber sheet comprises separate-type paper, reinforced rubber sheet basal body, enhancement layer successively.
25. according to the reinforced rubber sheet described in claim 23 or 24, it is characterized in that, described enhancement layer is a kind of in glasscloth, nylon fiber cloth, carbon cloth or synthetic resins non-woven fabrics.
26. 1 kinds of steel plate composite materials, this steel plate composite material comprises steel plate, the reinforced rubber sheet being bonded together successively, and described steel plate contacts with the reinforced rubber sheet basal body of reinforced rubber sheet, it is characterized in that, and described reinforced rubber sheet is the reinforced rubber sheet described in claim 23.
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| CN103992529A (en) * | 2014-04-29 | 2014-08-20 | 天长永泰密封材料有限公司 | Nitrile butadiene rubber sealant |
| CN104017530A (en) * | 2014-05-29 | 2014-09-03 | 浙江固特热熔胶有限公司 | Multi-function ship bottom sealant and production method thereof |
| CN105385367A (en) * | 2015-12-10 | 2016-03-09 | 苏州爱盟机械有限公司 | Reinforcing rubber sheet |
| WO2016183580A1 (en) * | 2015-05-14 | 2016-11-17 | Zephyros, Inc. | Localized panel stiffener |
| CN108530836A (en) * | 2018-04-18 | 2018-09-14 | 浙江吉利汽车有限公司 | A kind of low temperature reinforcement liner plate composite material and its low temperature reinforcement liner plate |
| CN108546390A (en) * | 2018-04-20 | 2018-09-18 | 江苏同盟汽车零部件实业有限公司 | A kind of high reinforcement multiple reinforcing chip of automobile and preparation method thereof |
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Cited By (10)
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| CN103992529A (en) * | 2014-04-29 | 2014-08-20 | 天长永泰密封材料有限公司 | Nitrile butadiene rubber sealant |
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| WO2016183580A1 (en) * | 2015-05-14 | 2016-11-17 | Zephyros, Inc. | Localized panel stiffener |
| CN107810108A (en) * | 2015-05-14 | 2018-03-16 | 泽菲罗斯有限公司 | Local panel reinforcer |
| US10780672B2 (en) | 2015-05-14 | 2020-09-22 | Zephyros, Inc. | Localized panel stiffener |
| CN105385367A (en) * | 2015-12-10 | 2016-03-09 | 苏州爱盟机械有限公司 | Reinforcing rubber sheet |
| CN108530836A (en) * | 2018-04-18 | 2018-09-14 | 浙江吉利汽车有限公司 | A kind of low temperature reinforcement liner plate composite material and its low temperature reinforcement liner plate |
| CN108530836B (en) * | 2018-04-18 | 2021-03-23 | 浙江吉利汽车有限公司 | Composite material for low-temperature reinforced lining plate and low-temperature reinforced lining plate thereof |
| CN108546390A (en) * | 2018-04-20 | 2018-09-18 | 江苏同盟汽车零部件实业有限公司 | A kind of high reinforcement multiple reinforcing chip of automobile and preparation method thereof |
| CN111057476A (en) * | 2019-12-19 | 2020-04-24 | 常州英拓利汽车科技有限公司 | Steel plate reinforcing rubber sheet for vehicle and preparation method thereof |
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