CN105111984A - Environmental-friendly flame-retardant epoxy automobile hemming adhesive and preparation method therefor - Google Patents
Environmental-friendly flame-retardant epoxy automobile hemming adhesive and preparation method therefor Download PDFInfo
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- CN105111984A CN105111984A CN201510478077.4A CN201510478077A CN105111984A CN 105111984 A CN105111984 A CN 105111984A CN 201510478077 A CN201510478077 A CN 201510478077A CN 105111984 A CN105111984 A CN 105111984A
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Abstract
The invention relates to an environmental-friendly flame-retardant epoxy automobile hemming adhesive and a preparation method therefor. The hemming adhesive comprises 10-40 parts of epoxy resin, 5-40 parts of modified epoxy resin, 0-3 parts of a coupling agent, 0-30 parts of a diluent, 0-8 parts of a flexibilizer, 2-10 parts of a curing agent, 10-20 parts of a flame retardant and 20-50 parts of filler. The preparation method comprises: adding 10-40 parts of epoxy resin, 5-40 parts of modified epoxy resin, 0-3 parts of the coupling agent, 0-30 parts of the diluent, 0-8 parts of the flexibilizer, 2-10 parts of the curing agent, 10-20 parts of the flame retardant and 20-50 parts of the filler in parts by weight into a twin planet power mixing stirrer to be mixed; vacuumizing the stirrer to (-0.1)-(-0.008)Mpa; and mechanically stirring the mixture for 1.5 hours under the condition that the autorotation rate of the twin planet power mixing stirrer is 500-1000 r/m and the speed of revolution is 5-8 r/m, and discharging the mixture to obtain the automobile hemming adhesive.
Description
Technical field
The present invention relates to a kind of Environment-friendlyflame-retardant flame-retardant fold adhesive and preparation method thereof, be applied in a kind of hot setting epoxy structural rubber on automobile welding process, belong to single-component epoxy glue technical field.
Background technology
Along with development and the performance requriements that improves constantly of auto manufacturing technology, the application of tackiness agent is more and more extensive, and kind is day by day complete, and automobile folding adhesive is the important glue kind of a class be wherein applied on automobile welding process.This glue is mainly used in the bonding of the flanging positions such as car door, engine bonnet, luggage-boot lid, not only play replacement spot welding, eliminate pit, ensure the effect that vehicle body is smoothly attractive in appearance, structure, sealing car body can also be strengthened, and prevent the generation of bonding site corrosion too early because paint cannot be coated onto.
Epoxy resin folding adhesive is because of its excellent in mechanical performance, environmental protection, cost is low, it is the main folding adhesive type of domestic and international automaker, as red flag, Buick, Audi etc., in recent years, the domestic research to automobile folding adhesive, mainly concentrate on mechanical property, less to the research of the closely-related flame retardant properties of car safety environmental-protecting performance.
At present, both at home and abroad to the environmental requirement special concern to automotive industry auxiliary products of environmental issue growing interest, particularly European countries, a lot of full-sized car manufacturers explicitly calls for the material prohibitting the use and be harmful to environment or human body to its auxiliary products.Clearly limit as the use material of french citroen company to automobile accessories product has done, as materials such as Polybrominated biphenyl, Poly Brominated Diphenyl Ethers, glycols, the different new ester of phthalic acid two, cadmium, mercury, lead, sexavalent chromes.Wherein, Polybrominated biphenyl, Poly Brominated Diphenyl Ethers are prohibited from using as important fire retardant material; In addition, the flame retardant properties of conventional flame retardant declines, and needs just can reach flame retardant effect by adding in a large number, but has a strong impact on product performance, especially mechanical property.Can not improve product mechanical property and environmental protection flame retardant performance, be a weak link of domestic folding adhesive development simultaneously.
Therefore, a kind of environmental protection flame retardant is developed and the automobile folding adhesive of good mechanical performance is very necessary.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to solve the problem that existing epoxy resin folding adhesive can not have better product mechanical property and environmental protection flame retardant performance simultaneously.
To achieve these goals, technical solution of the present invention is: a kind of environmental protection flame retardant epoxies automobile folding adhesive, this tackiness agent is epoxy binder in monocomponent in, by weight, composition comprises following component and proportioning: epoxy resin 10-40 part, modified epoxy 5-40 part, coupling agent 0-3 part, thinner 0-30 part, toughner 0-8 part, solidifying agent 2-10 part, fire retardant 10-20 part, filler 20-50 part.
Described epoxy resin is glycidyl ether type epoxy resin, Racemic glycidol lipid epoxy resin, glycidyl amine epoxy resin, cycloaliphatic epoxy resin or its composition; Described modified epoxy be nano-rubber modified epoxy, carboxylic acrylonitrile butadiene rubber modified epoxy resin one wherein or its compositely to form; Described coupling agent be selected from silane coupling agent, titanate coupling agent wherein a kind of or its compositely to form; Described thinner is common commercially available thinner, and its effect reduces system viscosity, makes processing ease; Described toughner is selected from polyether glycol 2000, polyether glycol 4000, CYH-277, can increase the toughness of epoxy resin cured product, improves shock strength and wear resistance, increases stripping strength and the shearing resistance of epoxy adhesive; Described solidifying agent is selected from guanidine and derivative, urea and derivative thereof, imidazole and its derivants, organic hydrazides and composition wherein one or more thereof; Described fire retardant material is selected from red phosphorus combustion inhibitor or take N, P as the expanded polystyrene veneer environmental protection fire retarding agent of main ignition-proof element; Described filler is metal oxide, carbonate, vitriol, silicon powder, silicate or its composition or be selected from nano titanium oxide, nano silicon, nano-calcium carbonate, nano aluminium oxide etc., can improve the effect of cured article toughness to a certain extent;
The beneficial effect that technical solution of the present invention is brought is: the present invention is directed to epoxy folding adhesive weak point and provide a kind of environmental protection flame retardant, the automobile folding adhesive of good mechanical performance, by adding a certain amount of special fire retardant, obviously improving flame retardant properties.Environment-friendlyflame-retardant flame-retardant fold adhesive prepared by the present invention, this Environment-friendlyflame-retardant flame-retardant fold adhesive shearing resistance and T stripping strength all meet sqtructural adhesive requirement, toughness is better, and meet environmental requirement, excellent flame retardancy, reach from fire combustion time≤2s, and good mechanical performance, shearing resistance 21Mpa, conservation rate 97.3%, T stripping strength 211N/25mm, conservation rate 97.1%, and raw material is all product common on market, simple and easy to get, cost is lower.
Embodiment
Below by way of specific embodiment, technical solution of the present invention is described further.
Embodiment 1
The environmental protection flame retardant epoxies automobile folding adhesive of the present embodiment, this tackiness agent is epoxy binder in monocomponent in, by weight, composition comprises following component and proportioning: epoxy resin 10 parts, modified epoxy 5 parts, coupling agent 3 parts, thinner 30 parts, toughner 8 parts, 2 parts, solidifying agent, fire retardant 10 parts, filler 20 parts.Described epoxy resin is glycidyl ether type epoxy resin, Racemic glycidol lipid epoxy resin, glycidyl amine epoxy resin, cycloaliphatic epoxy resin or its composition; Described modified epoxy be nano-rubber modified epoxy, carboxylic acrylonitrile butadiene rubber modified epoxy resin one wherein or its compositely to form; Described coupling agent be selected from silane coupling agent, titanate coupling agent wherein a kind of or its compositely to form; Described thinner is common commercially available thinner, and its effect reduces system viscosity, makes processing ease; Described toughner is selected from polyether glycol 2000, polyether glycol 4000, CYH-277, can increase the toughness of epoxy resin cured product, improves shock strength and wear resistance, increases stripping strength and the shearing resistance of epoxy adhesive; Described solidifying agent is selected from guanidine and derivative, urea and derivative thereof, imidazole and its derivants, organic hydrazides and composition wherein one or more thereof; Described fire retardant material is selected from red phosphorus combustion inhibitor or take N, P as the expanded polystyrene veneer environmental protection fire retarding agent of main ignition-proof element; Described filler is metal oxide, carbonate, vitriol, silicon powder, silicate or its composition or be selected from nano titanium oxide, nano silicon, nano-calcium carbonate, nano aluminium oxide etc., can improve the effect of cured article toughness to a certain extent.
When producing the present embodiment Environment-friendlyflame-retardant flame-retardant fold adhesive, said components is mixed by adding in double-planet dynamic mixing stirrer after above-mentioned formula rate mixing, be evacuated to-0.1 ~-0.008Mpa, it is 500 ~ 1000 revs/min at described double-planet dynamic mixing stirrer rotational velocity, revolution speed is under the condition of 5 ~ 8 revs/min, and mechanical stirring 1.5 hours, is uniformly dispersed through being stirred to, discharging, obtains described automobile folding adhesive.It is up to standard that the present invention makes the environmental-protecting performance of automobile folding adhesive require, matrix resin adopts common bisphenol A type epoxy resin simultaneously, and easily, market is easily purchased, easy to use in source.
The Environment-friendlyflame-retardant flame-retardant fold adhesive of the present embodiment, strictly controls prohibiting regulated substance in Industrial products, as: the different new ester of Polybrominated biphenyl, Poly Brominated Diphenyl Ethers, glycols, phthalic acid two, cadmium, mercury, lead, sexavalent chrome.
The Environment-friendlyflame-retardant flame-retardant fold adhesive excellent property of the present embodiment, select inorganic phosphorus flame retardant or take N, P as the expanded polystyrene veneer environmental protection fire retarding agent of main ignition-proof element, have good flame retardation effect, Heat stability is good, non-volatile, do not produce that corrosive gases, effect are lasting, low toxin.
The Environment-friendlyflame-retardant flame-retardant fold adhesive excellent property of the present embodiment, uses fire retardant addition selected by the present invention little, little to product Effect on Mechanical Properties, and ordinary epoxy resin and modified epoxy are with the use of, automobile folding adhesive good mechanical performance.
The Environment-friendlyflame-retardant flame-retardant fold adhesive of the present embodiment is mainly used in the bonding of the flanging position such as car door, engine bonnet, luggage of automobile.
Embodiment 2
Substantially the same manner as Example 1, the environmental protection flame retardant epoxies automobile folding adhesive of the present embodiment, component and proportioning: epoxy resin 25 parts, modified epoxy 23 parts, coupling agent 2 parts, thinner 15 parts, toughner 4 parts, 6 parts, solidifying agent, fire retardant 15 parts, filler 35 parts.
Embodiment 3
Substantially the same manner as Example 1, the environmental protection flame retardant epoxies automobile folding adhesive of the present embodiment, component and proportioning: epoxy resin 40 parts, modified epoxy 40 parts, coupling agent 3 parts, thinner 30 parts, toughner 8 parts, 10 parts, solidifying agent, fire retardant 20 parts, filler 50 parts.
Embodiment 4
Substantially the same manner as Example 1, the environmental protection flame retardant epoxies automobile folding adhesive of the present embodiment, component and proportioning: epoxy resin 10 parts, modified epoxy 5 parts, 2 parts, solidifying agent, fire retardant 10 parts, filler 20 parts.
Embodiment 5
Substantially the same manner as Example 1, the environmental protection flame retardant epoxies automobile folding adhesive of the present embodiment, component and proportioning: epoxy resin 13 parts, modified epoxy 13 parts, thinner 13 parts, toughner 3 parts, 2 parts, solidifying agent, fire retardant 13 parts, filler 26 parts.
Embodiment 6
Substantially the same manner as Example 1, the environmental protection flame retardant epoxies automobile folding adhesive of the present embodiment, component and proportioning: epoxy resin 26 parts, modified epoxy 13 parts, coupling agent 1 part, thinner 13 parts, toughner 5 parts, 4 parts, solidifying agent, fire retardant 13 parts, filler 26 parts.
Embodiment 7
Substantially the same manner as Example 1, the environmental protection flame retardant epoxies automobile folding adhesive of the present embodiment, component and proportioning: epoxy resin 33 parts, modified epoxy 15 parts, coupling agent 1 part, thinner 13 parts, toughner 3 parts, 7 parts, solidifying agent, fire retardant 13 parts, filler 30 parts.
The invention solves existing folding adhesive and there is the problems such as environmental protection index is on the low side, glue-applying technique poor performance, the shelf lives is short, modulus is low, wet-hot aging performance is poor.
The above embodiments of the invention scheme; all can only think explanation of the present invention and the present invention can not be limited; claims indicate protection scope of the present invention; any ratio in any suitable implication and scope changes; if do not bring other significant, unexpected effects, all should think and be also included within the scope of these claims.
Claims (10)
1. an environmental protection flame retardant epoxies automobile folding adhesive, it is characterized in that: it is epoxy binder in monocomponent in, by weight, following component and proportioning is comprised: epoxy resin 10-40 part, modified epoxy 5-40 part, coupling agent 0-3 part, thinner 0-30 part, toughner 0-8 part, solidifying agent 2-10 part, fire retardant 10-20 part, filler 20-50 part.
2. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: described epoxy resin be glycidyl ether type epoxy resin, Racemic glycidol lipid epoxy resin, glycidyl amine epoxy resin, cycloaliphatic epoxy resin wherein one or more.
3. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: described modified epoxy be nano-rubber modified epoxy, carboxylic acrylonitrile butadiene rubber modified epoxy resin wherein a kind of or its compositely to form.
4. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: described coupling agent be selected from silane coupling agent, titanate coupling agent wherein a kind of or its compositely to form.
5. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: described thinner is common commercially available thinner.
6. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: described toughner is selected from one or more in polyether glycol 2000, polyether glycol 4000, CYH-277.
7. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: described solidifying agent is selected from guanidine and derivative, urea and derivative thereof, imidazole and its derivants, organic hydrazides and composition wherein one or more thereof.
8. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: the expanded polystyrene veneer environmental protection fire retarding agent that described fire retardant material is selected from red phosphorus combustion inhibitor, N, P are main ignition-proof element wherein a kind of or its compositely to form.
9. environmental protection flame retardant epoxies automobile folding adhesive according to claim 1, is characterized in that: described filler is metal oxide, carbonate, vitriol, silicon powder, silicate or be selected from nano titanium oxide, nano silicon, nano-calcium carbonate, nano aluminium oxide wherein one or more.
10. the environmental protection flame retardant epoxies automobile folding adhesive that one of manufacturing claims 1 to 9 is described, is characterized in that, comprise the following steps:
By weight, epoxy resin 10-40 part, modified epoxy 5-40 part, coupling agent 0-3 part, thinner 0-30 part, toughner 0-8 part, solidifying agent 2-10 part, fire retardant 10-20 part, filler 20-50 part are added in double-planet dynamic mixing stirrer and mixes, be evacuated to-0.1 ~-0.008Mpa, it is 500 ~ 1000 revs/min at described double-planet dynamic mixing stirrer rotational velocity, revolution speed is under the condition of 5 ~ 8 revs/min, mechanical stirring 1.5 hours, discharging, obtains described automobile folding adhesive.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510478077.4A CN105111984A (en) | 2015-08-06 | 2015-08-06 | Environmental-friendly flame-retardant epoxy automobile hemming adhesive and preparation method therefor |
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| CN201510478077.4A CN105111984A (en) | 2015-08-06 | 2015-08-06 | Environmental-friendly flame-retardant epoxy automobile hemming adhesive and preparation method therefor |
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| CN105111984A true CN105111984A (en) | 2015-12-02 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243632A (en) * | 2016-08-04 | 2016-12-21 | 吴美燕 | A kind of preparation method of fire proofing material |
| CN106284711A (en) * | 2016-08-04 | 2017-01-04 | 吴美燕 | A kind of preparation method of fireproof heated board |
| CN108865033A (en) * | 2018-08-06 | 2018-11-23 | 济南汉斯曼时代技术有限公司 | A kind of high removing toughness folding adhesive and preparation method thereof |
| CN109513868A (en) * | 2018-10-23 | 2019-03-26 | 中国第汽车股份有限公司 | A kind of viscous composite connecting method of passenger car aluminum alloy engine hood riveting |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022929A1 (en) * | 2001-09-05 | 2003-03-20 | Hitachi Chemical Co., Ltd. | Flame-retardant heat-resistant resin composition and adhesive film comprising the same |
| CN104312512A (en) * | 2014-11-17 | 2015-01-28 | 南京艾布纳密封技术有限公司 | Environmentally friendly flame retardant epoxy automobile hemming adhesive and preparation method thereof |
-
2015
- 2015-08-06 CN CN201510478077.4A patent/CN105111984A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003022929A1 (en) * | 2001-09-05 | 2003-03-20 | Hitachi Chemical Co., Ltd. | Flame-retardant heat-resistant resin composition and adhesive film comprising the same |
| CN104312512A (en) * | 2014-11-17 | 2015-01-28 | 南京艾布纳密封技术有限公司 | Environmentally friendly flame retardant epoxy automobile hemming adhesive and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243632A (en) * | 2016-08-04 | 2016-12-21 | 吴美燕 | A kind of preparation method of fire proofing material |
| CN106284711A (en) * | 2016-08-04 | 2017-01-04 | 吴美燕 | A kind of preparation method of fireproof heated board |
| CN106243632B (en) * | 2016-08-04 | 2018-07-13 | 汕头市天凌安防科技有限公司 | A kind of preparation method of fire proofing material |
| CN106284711B (en) * | 2016-08-04 | 2018-10-19 | 秦恒建设发展有限公司 | A kind of preparation method of fireproof heated board |
| CN108865033A (en) * | 2018-08-06 | 2018-11-23 | 济南汉斯曼时代技术有限公司 | A kind of high removing toughness folding adhesive and preparation method thereof |
| CN109513868A (en) * | 2018-10-23 | 2019-03-26 | 中国第汽车股份有限公司 | A kind of viscous composite connecting method of passenger car aluminum alloy engine hood riveting |
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Application publication date: 20151202 |