CN1800290A - Flame-proof low-smoke low-toxicity epoxy adhesive - Google Patents
Flame-proof low-smoke low-toxicity epoxy adhesive Download PDFInfo
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- CN1800290A CN1800290A CN 200610018183 CN200610018183A CN1800290A CN 1800290 A CN1800290 A CN 1800290A CN 200610018183 CN200610018183 CN 200610018183 CN 200610018183 A CN200610018183 A CN 200610018183A CN 1800290 A CN1800290 A CN 1800290A
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Abstract
The invention relates to a flame-proof adhesive, wherein the raw material comprises the following constituents (by mass portions): epoxy resin 100 parts, hardening agent 10-100 parts, flame-proof filling material 50-259 parts, smoke inhibiting agent 10-30 parts, combustion inhibitor surface modifier 0.5-10 parts, deflocculating agent 5-40 parts, solidification promoter 0.1-10 parts, the solidification promoter can be one of modified amine solidifying agent or liquid state low-molecular-weight polyamide solidifying agent, or their mixture by any proportion.
Description
Technical field
The present invention relates to a kind of flame-retarding adhesive, be specifically related to the epoxy adhesive of a kind of fire-retardant, low cigarette, low toxicity.
Background technology
Along with the high stratification of building, automobile lightweight, high-newization of electrical equipment, superior, industrial large-sizedization of furniture, and the modernized trend of aerospace, shipbuilding and national defense industry, the various tackiness agent of multifunctional high-performance have obtained using widely day by day in each field of modern industry, and tackiness agent has become modern industry and the indispensable a kind of material of national defense industry.In traditional organic polymer tackiness agent, all adopted organic solvents such as benzene,toluene,xylene as solvent basically, there is toxicity problem; On the other hand, organic polymer tackiness agent great majority are more inflammable, have fire hazard, and organic adhesion agent the time also can produce smog and poison gas in burning, bring disaster to environment, the infringement HUMAN HEALTH.Along with science and technology development and progress, people have proposed more and more higher requirement to fire retardant material, not only require the high and low poison of flame retarding efficiency or nontoxic, press down cigarette, and require environmental friendliness, to recycle performance good.Therefore, research and development have fire-retardant, as to press down cigarette, low toxicity or nontoxic performance tackiness agent has become one of focus direction of development of new tackiness agent.
Domestic flame-retarding adhesive kind is few, quantity is few, application is few, with to compare gap abroad bigger.From preventing fire and guarantee security consideration that fire-retardant is a big good plan that prevents fire, is the major action of the protection mankind and environment.Therefore it is imperative to develop the flame retardant resistance tackiness agent energetically in China, and it is in the right season to provide for a rainy day.At present, fire retardant can be divided into organic and inorganic two big classes, and organic class comprises halogen system (bromine system and chlorine system), halogen-phosphorus system etc.; Mineral-type comprises silicon system, antimony system, aluminium system, magnesium system, boron system, molybdenum system etc.The flame retarding efficiency of halogenated flame retardant is higher, addition required in the material is also less, but general Halogen fire retardant material can discharge harmful poisonous corrosive gasess such as a large amount of smog and hydrogenchloride, prussic acid, vinylbenzene when presence of fire, can bring very big infringement to personnel and precision instrument.Therefore, great popular demand in the whole world for fire retardant material non-halogen, and some transnational flame retarded polymeric material suppliers also begin to provide halogen-free fire-resistant engineering plastics to market.In Europe, Dioxin (Dioxins, a kind of environment and HUMAN HEALTH are caused the carcinogenic substance that has a strong impact on) problem makes halogenated flame retardant and fire-retardant superpolymer thereof fail to obtain the environmental protection sign.So some European countries is limited the use of halogenated flame retardant at present, try hard to promote the non-halogen process of fire retardant material.What usage quantity was maximum in inorganic flame retardant is aluminium hydroxide, magnesium hydroxide and weisspiessglanz etc.The security of inorganic combustion inhibitor is higher, can not produce poisonous and corrosive gases, belongs to the physiology innoxious substance, and environmentally friendly, and effect is lasting, and is cheap, is the main developing direction of present fire retardant material.But the fill-up of single inorganic fire-retarded filler in polymer matrix composite could produce flame retardant effect when big, though satisfied the decline that the flame retardant effect of polymer composites can influence material such as mechanical property simultaneously like this.
Summary of the invention
The object of the present invention is to provide the epoxy adhesive of a kind of fire-retardant, low cigarette, low toxicity.
To achieve these goals, technical scheme of the present invention is: a kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it is characterized in that it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, presses down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material and make, the shared mass fraction of each raw material is: 100 parts of Resins, epoxy, 10～100 parts in solidifying agent, 50～250 parts of flame-retardant smoke inhibition fillers, press down 10～30 parts of fumicants, 0.5～10 part of fire retardant surface-modifying agent, 5～40 parts of thinners, 0.1～10 part of curing catalyst.
Described Resins, epoxy is for Resins, epoxy commonly used, as Resins, epoxy E-51, epoxy resin E-44, Resins, epoxy E-20 etc.
Described solidifying agent is low toxicity or nontoxic modified amine curing agent, any or two kinds in the liquid low molecular polyamides class solidifying agent, two kinds when mixing, is any proportioning.Low toxicity or nontoxic modified amine curing agent are N-hydroxyethyl-ethylenediamine (the extremely low LD of 120 solidifying agent, toxicity
504032mg/kg), the amine that contracts-105 epoxy hardener (low toxicity, LD
50＞3493mg/kg), phenol aldehyde modified amine solidifies and to cut [T
31Solidifying agent, nontoxic), GY-051 contract amine hardener (low toxicity, LD
503493mg/kg), in the SK-302 modified amine curing agent (smell is little, low toxicity) etc. any or mix more than two kinds and two kinds, when two or more mixes, be any proportioning.Liquid low molecular polyamides class solidifying agent be in 203 low molecular polyamides, 300 low molecular polyamides, 3051 low molecular polyamides, 650 low molecular polyamides etc. any or mix more than two kinds and two kinds, when two or more mixes, be any proportioning.
Described flame-retardant smoke inhibition filler is Al (OH)
3, Mg (OH)
2, Sb
2O
3, CaCO
3, among the ZnO any, perhaps be Al (OH)
3With Mg (OH)
2, Sb
2O
3, CaCO
3, any one or more than one mixing among the ZnO, during mixing, Sb wherein
2O
3, CaCO
3Or/and ZnO (adopt " with " time, i.e. Sb
2O
3, CaCO
3, mix more than two kinds and two kinds arbitrarily among the ZnO, when two or more mixes, be any proportioning) consumption be Al (OH)
3And Mg (OH)
20～5% of total consumption, and comprise the end points ratio, Al (OH)
3: Mg (OH)
2Be 1: (0～0.3), and comprise the end points ratio.The particle diameter of flame-retardant smoke inhibition filler is 2.5 * 10
-6Below the m.
But described fumicants is Al (OH)
3, Mg (OH)
2, molybdenum system press down in the fumicants any or mix more than two kinds and two kinds, when two or more mixes, be any proportioning.
It is the molybdenum based compound that described molybdenum system presses down fumicants, perhaps molybdenum based compound and metal oxide, and the quality proportioning of molybdenum based compound and metal oxide is: 1: (0～1), and comprise the end points ratio.The molybdenum based compound is molybdic oxide, calcium molybdate or zinc molybdate; Metal oxide is cupric oxide or ferric oxide.
Described anti-flaming smoke-inhibiting agent surface-modifying agent is any or two kinds among organo silane coupling agent KH-550, organo silane coupling agent KH-560, organo silane coupling agent KH-540, organo silane coupling agent KH-590, organo silane coupling agent G-407, organo silane coupling agent G-402, the titanate coupling agent OL-T999 and mixes more than two kinds arbitrarily, any two kinds or any when mixing more than two kinds, be any proportioning.
Described thinner is any or two kinds in 662 thinners (glycerine epoxy), 680 thinners (resorcinol diglycidyl ether), X-52 epoxide resin reactive diluent (cresylglycidylether), thinner ZH-16 (hexanediol diglycidyl ether), 501 thinners (epoxy propane butyl ether) and mixes more than two kinds arbitrarily, any two kinds or any when mixing more than two kinds, be any proportioning.
Described curing catalyst is any or the two kinds of mixing in Dyhard RU 100, the meta-cresol, two kinds when mixing, is any proportioning.
It is the adhesive matrix material that the present invention adopts by Resins, epoxy, add solidifying agent, flame-retardant smoke inhibition filler, fire retardant surface-modifying agent, thinner and curing catalyst raw material and make, thereby make the epoxy adhesive that obtains have fire-retardant, low cigarette, low toxicity and high-intensity performance.The present invention adopts the flame-retardant smoke inhibition filler, has fire retardation; The present invention cooperates and presses down fumicants, also has the cigarette effect of pressing down; Solidifying agent, flame-retardant smoke inhibition filler, fire retardant surface-modifying agent, thinner and curing catalyst raw material that the present invention adopts are low toxicity or nontoxic, and the present invention has the characteristics of low toxicity.By fire retardant surface-modifying agent (being coupling agent) fire retardant is carried out surface modification, thereby improve the interface compatibility (being interface binding power) that makes resin and inorganic anti-flaming smoke-inhibiting agent (flame-retardant smoke inhibition filler) greatly, thereby make tackiness agent have higher bonding strength, performances such as its resistance to acids and bases, oil-proofness, water tolerance, thermotolerance, radiation resistance are all better.
The hypotoxicity of flame-retarding adhesive from construction and when burning two aspects consider, require hypotoxicity in the construction process of tackiness agent on the one hand, promptly the construction workman is not had the physiology toxic action; On the other hand, under presence of fire incendiary situation, can not produce deleterious product, as toxic gas and smog etc.From prescription of the present invention, can know that the toxicity of tackiness agent mainly comes from solidifying agent, especially amine curing agent is the toxic main source of uncured epoxyn, both at home and abroad the toxicity problem of solidifying agent is attached great importance at present, it is strong day by day to require to solve the toxic cry of solidifying agent.Having more highly toxic amine curing agent and carry out modification original, is to reduce solidifying agent toxicity and implement nontoxic most important approach.Use the very low modified amine curing agent of toxicity among the present invention, its curing speed also lower molecular weight polymeric amide wants fast relatively, but does not have low molecular polyamides good to the toughening effect of epoxy.Here their The combined can be used, can make tackiness agent have higher curing speed on the one hand, also can carry out on the other hand epoxy toughness reinforcing, to reduce the excessive fragility of epoxy.
Utilize low molecular polyamides as curing agent for epoxy resin, can also play toughening effect, but its curing speed is slower epoxy, at low temperatures especially, so must add curing catalyst to improve its curing speed and low-temperature curing performance.In addition, also can add the modified amine curing agent of low toxicity, also can reach the curing speed that improves the low molecular polyamides curing system.
The present invention can adopt Al (OH) separately
3The flame-retardant smoke inhibition filler, can also adopt composite flame-proof press down the cigarette filler [two or more, as Al (OH)
3And Mg (OH)
2], can make flame-retarding adhesive have beyond thought performance, for example, Al (OH)
3(ATH) decomposition temperature is 205 ℃, Mg (OH)
2(MH) decomposition temperature is 320 ℃, with both and time spent, then can remedy the defective that ATH causes Flame Retardancy to descend because of its decomposition temperature is lower, and can make composite flame-proof press down the cigarette filler in the material oxidation decomposition course, in 235～455 ℃ scope, all there is the dehydration thermo-negative reaction, therefore can in wide temperature range, effectively suppresses the burning of polymer materials.In addition, Al (OH)
3And Mg (OH)
2Be not only a kind of fire retardant material, but also all have smoke suppressing effect: they all are amphoteric hydroxides, can with acid and alkali substance in the smog (as HCl, NH
3) wait effect, form the less salt of volatility, thereby reach the effect that presses down cigarette.
Except fire-retardant, pressing down cigarette also is of the present invention one big emphasis.Al (OH) here
3And Mg (OH)
2Itself promptly be fire retardant, also can play the effect that presses down cigarette and filling, promptly play fire-retardant, as to press down cigarette and filling triple role.Because Al (OH)
3And Mg (OH)
2Itself have the triple role that flame-retardant smoke inhibition is filled, thus their consumption also can be strengthened, and press down fumicants without molybdenum system.The toxicity that molybdenum system presses down fumicants is extremely low, the molybdenum based compound to press down the cigarette effect be to work in solid phase rather than in gas phase, be to promote the generation of charcoal layer and reduce the cigarette amount by Lewis acid or reductive coupling mechanism.Although the molybdenum based compound in detail press down cigarette mechanism can't be clear fully, it is fairly obvious with becoming the charcoal effect that its intensive presses down the cigarette effect.In addition, molybdenum based compound such as MoO
3When mixing use, press down the cigarette effect than single MoO with some metal oxide (as cupric oxide, ferric oxide)
3More obvious.The compound of iron (as ferrocene) also can play the effect that presses down cigarette, but it mainly is to be applied in the rigid PVC, other then also do not use reporting for work.Though the cigarette effect that presses down of iron cpd is to be worth sure, but they are limited in industrial application, this is because the color problem of this compounds on the one hand, be that they may play fire-retardant the oxidizing reaction of heat release (owing to cause) on the other hand, thereby make iron cpd is pressed down fumicants not to promote as polymkeric substance.Can also cooperate the mixture that adds the molybdenum based compound or form with some metal oxide for pressing down fumicants among the present invention.
The flame retardant properties of polymer materials has much relations with the particle diameter of fire-retardant filler wherein, and along with attenuating of granularity, the limiting oxygen index(LOI) of polymer materials will rise, thereby improve its flame retardant properties.What secondly, the super-refinement of flame-retardant smoke inhibition filler also helped synthetic materials slickness and mechanical property improves that (particle diameter of flame-retardant smoke inhibition filler is 2.5 * 10
-6M is following), sometimes even can also play and strengthen toughness reinforcing function.The particle diameter of flame-retardant smoke inhibition filler is more little, particle will easy more dispersion in matrix resin, the small particle size inorganic filler particle is with respect to the particle of big particle diameter, its few surface defects, the non-matching atom is many, just big with polymkeric substance generation physics or chemically combined possibility, this will help to improve the bonding force of filler grain and substrate ring epoxy resins from this respect.What solve to some degree here is exactly the interface problem of matrix material, and this has certain positive meaning for the bonding strength that improves epoxy adhesive.Said above that because the consumption of inorganic fire-retarded filler in epoxy adhesive crossed the decline that conference causes its mechanical property, for tackiness agent, its bonding strength was its most important mechanical performance index.As mentioned above, the super-refinement of fire-retardant filler particle helps improving the mechanical property of tackiness agent, but this also is nowhere near.Because ultra-fine inorganic fire retardant powder is different fully with the interfacial property of tackiness agent organic polymer matrix, its consistency is relatively poor, and directly interpolation or excessive use often cause some physical and mechanical property of base material to descend.Therefore also should carry out surface modification, thereby improve the consistency of filler grain and substrate ring epoxy resins, increase its bonding force the inorganic fire-retarded particle of super-refinement.In the use of tackiness agent, generally adopt the coupling agent method in the chemical surface modification, for example can utilize organo silane coupling agent, titanate coupling agent or higher fatty acid an alkali metal salt analog anion surfactants etc. to ATH, MH, Sb
2O
3Carry out surface modification, improve the consistency of they and substrate ring epoxy resins, improve the physical and mechanical property of tackiness agent.And, by the inorganic combustion inhibitor particle is carried out surface modification, also help to improve the dispersiveness of inorganic combustion inhibitor particle in resin matrix, thereby also can help to improve its flame retardant properties.Facts have proved that through the inorganic fire-retarded system after super-refinement and the surface treatment, its over-all properties is not greatly improved before handling.
Because the general viscosity of Resins, epoxy is all bigger, the epoxy adhesive that fits in too, excessive viscosity has seriously influenced the workability of tackiness agent.But the common organic solvents such as three benzene solvents that tackiness agent is commonly used are all poisonous, and are harmful to environment and construction workman, should not adopt.The present invention here adopts the solvent of the difficult evaporable innoxious solvent of the lower molecular weight with epoxide group as tackiness agent, Here it is epoxide resin reactive diluent, it can improve the construction technology of tackiness agent on the one hand, increase its wetting property to adherend, thereby raising bonding strength, can also strengthen amount of filler, prolong the working life of tackiness agent etc.It also participates in the curing reaction of Resins, epoxy on the other hand, and what negative influence tackiness agent is not had.Because this tackiness agent has strict demand to toxicity, so thinner must low toxicity or nontoxic.
It is low that the present invention has viscosity, have good workability, volatility is low, toxicity is extremely low, substantially nontoxic characteristics during construction, reach more than the 20MPa through its metal to metal tensile shear strength after the self-vulcanizing, limiting oxygen index(LOI) reaches 65.4, maximum smoke density is 39.25, the cured article toxicity test meets the nontoxic requirement of FDA (standards of the nontoxic level foodstuff additive that U.S. food and Drug Administration include), and it is heat-resisting, water, oil, acid, alkali, vibration, radiance is all better, the bonding strength conservation rate reaches more than 95%, is a kind of highly effective flame-retardant that has, low cigarette, the environment-friendly type high performance tackiness agent of low toxicity.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:(all is as the criterion with mass parts, down together)
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: the liquid polymeric amide of 100,203 lower molecular weights: 40, organo silane coupling agent KH-580:2.5, organo silane coupling agent KH-590:1.2, super-refinement Al (OH)
3(be called for short ATH, below identical) powder: 240,662 thinners (glycerine epoxy): 25, meta-cresol curing catalyst: 5.Al (OH)
3Powder plays the flame-retardant smoke inhibition filler simultaneously and presses down the fumicants effect.Wherein super-refinement is meant that particle diameter is 2.5 * 10
-6Below the m.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: 100, the liquid polymeric amide of 203 lower molecular weights: 40, organo silane coupling agent KH-580:2.5, organo silane coupling agent KH-590:1.2, super-refinement ATH powder: 240,662 thinners (glycerine epoxy): 25, meta-cresol curing catalyst: 5, choose Resins, epoxy, the liquid polymeric amide of 203 lower molecular weights, organo silane coupling agent KH-580, organo silane coupling agent KH-590, super-refinement ATH powder, 662 thinners (glycerine epoxy), meta-cresol curing catalyst; 2, with Resins, epoxy, the liquid polymeric amide of 203 lower molecular weights, organo silane coupling agent KH-580, organo silane coupling agent KH-590, super-refinement ATH powder, 662 thinners (glycerine epoxy), the meta-cresol curing catalyst mixes, and gets product.
Embodiment 2:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: the liquid polymeric amide of 100,650 lower molecular weights: 80, organo silane coupling agent KH-550:3, super-refinement ATH powder: 160, super-refinement Mg (OH)
2Powder: 45, X-52 epoxide resin reactive diluent (cresylglycidylether): 5,662 thinners (glycerine epoxy): 30, Dyhard RU 100 curing catalyst: 7.Super-refinement ATH powder, super-refinement Mg (OH)
2Powder plays the flame-retardant smoke inhibition filler simultaneously and presses down the fumicants effect.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: the liquid polymeric amide of 100,650 lower molecular weights: 80, and organo silane coupling agent KH-550:3, super-refinement ATH powder: 160, super-refinement Mg (OH)
2Powder: 45, X-52 epoxide resin reactive diluent (cresylglycidylether): 5,662 thinners (glycerine epoxy): 30, the Dyhard RU 100 curing catalyst: 7, choose Resins, epoxy, the liquid polymeric amide of 650 lower molecular weights, organo silane coupling agent KH-550, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, X-52 epoxide resin reactive diluent (cresylglycidylether), 662 thinners (glycerine epoxy), Dyhard RU 100 curing catalyst; 2, with Resins, epoxy, the liquid polymeric amide of 650 lower molecular weights, organo silane coupling agent KH-550, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, X-52 epoxide resin reactive diluent (cresylglycidylether), 662 thinners (glycerine epoxy), Dyhard RU 100 curing catalyst mix, and get product.Wherein super-refinement is meant that particle diameter is 2.5 * 10
-6Below the m.
Embodiment 3:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: 100, the liquid polymeric amide of 650 lower molecular weights: 60, organo silane coupling agent KH-550:2, titanate coupling agent OL-T999:2, thinner ZH-16 (hexanediol diglycidyl ether): 15,501 thinners (epoxy propane butyl ether): 5, meta-cresol curing catalyst: 4, super-refinement ATH powder: 170, super-refinement Mg (OH)
2Powder: 40, Sb
2O
3: 10.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: 100, the liquid polymeric amide of 650 lower molecular weights: 60, organo silane coupling agent KH-550:2, titanate coupling agent OL-T999:2, thinner ZH-16 (hexanediol diglycidyl ether): 15,501 thinners (epoxy propane butyl ether): 5, meta-cresol curing catalyst: 4, super-refinement ATH powder: 170, super-refinement Mg (OH)
2Powder: 40, Sb
2O
3: 10, choose Resins, epoxy, the liquid polymeric amide of 650 lower molecular weights, organo silane coupling agent KH-550, titanate coupling agent OL-T999, thinner ZH-16 (hexanediol diglycidyl ether), 501 thinners (epoxy propane butyl ether), meta-cresol curing catalyst, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, Sb
2O
32, with Resins, epoxy, the liquid polymeric amide of 650 lower molecular weights, organo silane coupling agent KH-550, titanate coupling agent OL-T999, thinner ZH-16 (hexanediol diglycidyl ether), 501 thinners (epoxy propane butyl ether), meta-cresol curing catalyst, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, Sb
2O
3Mix, get product.
Embodiment 4:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: the liquid polymeric amide of 100,300 lower molecular weights: 40, organo silane coupling agent KH-580:2.5, organo silane coupling agent KH-590:1.2, super-refinement ATH powder: 220,662 thinners (glycerine epoxy): 25, the SK-302 modified amine curing agent: 7, MoO
3: 15, Fe
2O
3: 5.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: 100, the liquid polymeric amide of 300 lower molecular weights: 40, organo silane coupling agent KH-580:2.5, organo silane coupling agent KH-590:1.2, super-refinement ATH powder: 220,662 thinners (glycerine epoxy): 25, the SK-302 modified amine curing agent: 7, MoO
3: 15, Fe
2O
3: 5, choose Resins, epoxy, the liquid polymeric amide of 300 lower molecular weights, organo silane coupling agent KH-580, organo silane coupling agent KH-590, super-refinement ATH powder, 662 thinners (glycerine epoxy), SK-302 modified amine curing agent, MoO
3, Fe
2O
32, with the liquid polymeric amide of Resins, epoxy, 300 lower molecular weights, organo silane coupling agent KH-580, organo silane coupling agent KH-590,, super-refinement ATH powder, 662 thinners (glycerine epoxy), SK-302 modified amine curing agent, MoO
3, Fe
2O
3Mix, get product.
Embodiment 5:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: the liquid polymeric amide of 100,300 lower molecular weights: 40, organo silane coupling agent G-402:3.5, super-refinement ATH powder: 245,662 thinners (glycerine epoxy): 25, meta-cresol curing catalyst: 5.Super-refinement ATH powder plays the flame-retardant smoke inhibition filler simultaneously and presses down the fumicants effect.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: 100, the liquid polymeric amide of 300 lower molecular weights: 40, organo silane coupling agent G-402:3.5, super-refinement ATH powder: 245,662 thinners (glycerine epoxy): 25, the meta-cresol curing catalyst: 5, choose Resins, epoxy, the liquid polymeric amide of 300 lower molecular weights, organo silane coupling agent G-402, super-refinement ATH powder, 662 thinners (glycerine epoxy), meta-cresol curing catalyst; 2, with Resins, epoxy, the liquid polymeric amide of 300 lower molecular weights, organo silane coupling agent G-402, super-refinement ATH powder, 662 thinners (glycerine epoxy), meta-cresol curing catalyst mix, and get product.
Embodiment 6:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: 100, the liquid polymeric amide of 203 lower molecular weights: 60, organo silane coupling agent KH-550:4, thinner ZH-16 (hexanediol diglycidyl ether): 15,501 thinners (epoxy propane butyl ether): 1, the meta-cresol curing catalyst: 4, super-refinement ATH powder: 180, super-refinement Mg (OH)
2Powder: 30, Sb
2O
3: 10.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: 100, the liquid polymeric amide of 203 lower molecular weights: 60, organo silane coupling agent KH-550:4, thinner ZH-16 (hexanediol diglycidyl ether): 15,501 thinners (epoxy propane butyl ether): 1, the meta-cresol curing catalyst: 4, super-refinement ATH powder: 180, super-refinement Mg (OH)
2Powder: 30, Sb
2O
3: 10, choose Resins, epoxy, the liquid polymeric amide of 203 lower molecular weights, organo silane coupling agent KH-550, thinner ZH-16 (hexanediol diglycidyl ether), 501 thinners (epoxy propane butyl ether), meta-cresol curing catalyst, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, Sb
2O
32, with Resins, epoxy, the liquid polymeric amide of 203 lower molecular weights, organo silane coupling agent KH-550, thinner ZH-16 (hexanediol diglycidyl ether), 501 thinners (epoxy propane butyl ether), meta-cresol curing catalyst, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, Sb
2O
3Mix, get product.
Embodiment 7:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: 100, N-hydroxyethyl-ethylenediamine: 45, organo silane coupling agent KH-580:2.5, organo silane coupling agent KH-590:1.2, super-refinement ATH powder: 200, super-refinement Mg (OH)
2Powder: 40,662 thinners (glycerine epoxy): 25, the SK-302 modified amine curing agent: 5, MoO
3: 10, Fe
2O
3: 5.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: 100, and N-hydroxyethyl-ethylenediamine: 45, organo silane coupling agent KH-580:2.5, organo silane coupling agent KH-590:1.2, super-refinement ATH powder: 200, super-refinement Mg (OH)
2Powder: 40,662 thinners (glycerine epoxy): 25, the SK-302 modified amine curing agent: 5, MoO
3: 10, Fe
2O
3: 5, choose Resins, epoxy, N-hydroxyethyl-ethylenediamine, organo silane coupling agent KH-580, organo silane coupling agent KH-590,, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, 662 thinners (glycerine epoxy), SK-302 modified amine curing agent, MoO
3, Fe
2O
32, with Resins, epoxy, N-hydroxyethyl-ethylenediamine, organo silane coupling agent KH-580, organo silane coupling agent KH-590,, super-refinement ATH powder, super-refinement Mg (OH)
2Powder, 662 thinners (glycerine epoxy), SK-302 modified amine curing agent, MoO
3, Fe
2O
3Mix, get product.
Embodiment 8:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is:
Resins, epoxy: 100, N-hydroxyethyl-ethylenediamine: the liquid polymeric amide of 20,300 lower molecular weights: 20, organo silane coupling agent KH-590:3.2, super-refinement ATH powder: 240,680 thinners (resorcinol diglycidyl ether): 25, meta-cresol curing catalyst: 5.
Its preparation method is: 1, by the shared mass fraction of each raw material be: Resins, epoxy: 100, N-hydroxyethyl-ethylenediamine: 20, the liquid polymeric amide of 300 lower molecular weights: 20, organo silane coupling agent KH-590:3.2, super-refinement ATH powder: 240,680 thinners (resorcinol diglycidyl ether): 25, meta-cresol curing catalyst: 5, choose Resins, epoxy, N-hydroxyethyl-ethylenediamine, the liquid polymeric amide of 300 lower molecular weights, organo silane coupling agent KH-590, super-refinement ATH powder, 680 thinners (resorcinol diglycidyl ether), meta-cresol curing catalyst; 2, with Resins, epoxy, N-hydroxyethyl-ethylenediamine, the liquid polymeric amide of 300 lower molecular weights, organo silane coupling agent KH-590, super-refinement ATH powder, 680 thinners (resorcinol diglycidyl ether), the meta-cresol curing catalyst mixes, and gets product.
Embodiment 9:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is: 100 parts of Resins, epoxy, 10 parts in solidifying agent, 50 parts of flame-retardant smoke inhibition fillers, press down 10 parts of fumicants, 0.5 part of fire retardant surface-modifying agent, 5 parts of thinners, 0.1 part of curing catalyst.
Described Resins, epoxy is Resins, epoxy E-51 commonly used.Described solidifying agent is the amine that contracts-105 epoxy hardener (low toxicity, LD
50＞3493mg/kg).Described flame-retardant smoke inhibition filler is ZnO, and the particle diameter of flame-retardant smoke inhibition filler is 2.5 * 10
-6Below the m.But described fumicants is molybdenum based compound (molybdic oxide).Described anti-flaming smoke-inhibiting agent surface-modifying agent is organo silane coupling agent KH-550.Described thinner is 662 thinners (glycerine epoxies).Described curing catalyst is a Dyhard RU 100.
Its preparation method is the same.
Embodiment 10:
A kind of epoxy adhesive of flame-proof low-smoke low-toxicity, it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material makes, and the shared mass fraction of each raw material is: 100 parts of Resins, epoxy, 100 parts in solidifying agent, 250 parts of flame-retardant smoke inhibition fillers, press down 30 parts of fumicants, 10 parts of fire retardant surface-modifying agents, 40 parts of thinners, 10 parts of curing catalysts.
Described Resins, epoxy is epoxy resin E-44 commonly used.Described solidifying agent is phenol aldehyde modified amine curing agent (T
31Solidifying agent, nontoxic) and 203 low molecular polyamides, phenol aldehyde modified amine curing agent is that 50,203 low molecular polyamides are 50.
Described flame-retardant smoke inhibition filler is Al (OH)
3With Mg (OH)
2, Sb
2O
3Mix Al (OH)
3Be 220, Mg (OH)
2Be 25, Sb
2O
3Be 5; The particle diameter of flame-retardant smoke inhibition filler is 2.5 * 10
-6Below the m.
The described fumicants that presses down is that molybdic oxide and cupric oxide mix, and molybdic oxide is 15, and cupric oxide is 15.
Described anti-flaming smoke-inhibiting agent surface-modifying agent is titanate coupling agent OL-T99.
Described thinner is 501 thinners (epoxy propane butyl ethers).
Described curing catalyst is that Dyhard RU 100 and meta-cresol mix, and Dyhard RU 100 is 5, and meta-cresol is 5.
Its preparation method is the same.
Resins, epoxy of the present invention, solidifying agent, flame-retardant smoke inhibition filler, the bound value and the interval value that press down fumicants, fire retardant surface-modifying agent, thinner, curing catalyst raw material can both be realized the present invention, and solidifying agent, flame-retardant smoke inhibition filler, press down fumicants, fire retardant surface-modifying agent, thinner, each concrete raw material of curing catalyst and can both realize the present invention, just do not enumerate embodiment one by one at this.
Claims (9)
1. the epoxy adhesive of a flame-proof low-smoke low-toxicity, it is characterized in that it comprises Resins, epoxy, solidifying agent, flame-retardant smoke inhibition filler, presses down fumicants, fire retardant surface-modifying agent, thinner and curing catalyst raw material and make, the shared mass fraction of each raw material is: 100 parts of Resins, epoxy, 10～100 parts in solidifying agent, 50～250 parts of flame-retardant smoke inhibition fillers, press down 10～30 parts of fumicants, 0.5～10 part of fire retardant surface-modifying agent, 5～40 parts of thinners, 0.1～10 part of curing catalyst; Described solidifying agent is any or the two kinds of mixing in modified amine curing agent, the liquid low molecular polyamides class solidifying agent, two kinds when mixing, is any proportioning.
2. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 1, it is characterized in that: any in described modified amine curing agent is a N-hydroxyethyl-ethylenediamine, the amine that contracts-105 epoxy hardener, phenol aldehyde modified amine curing agent, GY-051 contract amine hardener or the SK-302 modified amine curing agent or mix more than two kinds and two kinds, when two or more mixes, be any proportioning.
3. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 1, it is characterized in that: described liquid low molecular polyamides class solidifying agent be in 203 low molecular polyamides, 300 low molecular polyamides, 3051 low molecular polyamides or 650 low molecular polyamides any or mix more than two kinds and two kinds, when two or more mixes, be any proportioning.
4. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 1, it is characterized in that: described flame-retardant smoke inhibition filler is Al (OH)
3, Mg (OH)
2, Sb
2O
3, CaCO
3, among the ZnO any, perhaps be Al (OH)
3With Mg (OH)
2, Sb
2O
3, CaCO
3, any one or more than one mixing among the ZnO, during mixing, Sb wherein
2O
3, CaCO
3Or/and the consumption of ZnO is Al (OH)
3And Mg (OH)
20～5% of total consumption, Al (OH)
3: Mg (OH)
2Be 1: 0～0.3.
5. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 1 is characterized in that: described to press down fumicants be Al (OH)
3, Mg (OH)
2, molybdenum system press down in the fumicants any or mix more than two kinds and two kinds, when two or more mixes, be any proportioning.
6. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 5, it is characterized in that: it is the molybdenum based compound that described molybdenum system presses down fumicants, perhaps molybdenum based compound and metal oxide, the quality proportioning of molybdenum based compound and metal oxide is: 1: 0～1; Wherein the molybdenum based compound is molybdic oxide, calcium molybdate or zinc molybdate, and metal oxide is cupric oxide or ferric oxide.
7. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 1, it is characterized in that: described fire retardant surface-modifying agent is any or two kinds among organo silane coupling agent KH-550, organo silane coupling agent KH-560, organo silane coupling agent KH-580, organo silane coupling agent KH-590, organo silane coupling agent G-407, organo silane coupling agent G-402, the titanate coupling agent OL-T999 or mixes more than two kinds arbitrarily, any two kinds or any when mixing more than two kinds, be any proportioning.
8. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 1, it is characterized in that: described thinner is any or two kinds in 662 thinners, 680 thinners, X-52 epoxide resin reactive diluent, thinner ZH-16,501 thinners or mixes more than two kinds arbitrarily, any two kinds or any when mixing more than two kinds, be any proportioning.
9. the epoxy adhesive of a kind of flame-proof low-smoke low-toxicity according to claim 1 is characterized in that: described curing catalyst is any or the two kinds of mixing in Dyhard RU 100, the meta-cresol, two kinds when mixing, is any proportioning.
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|---|---|---|---|
| CNB2006100181835A CN100375772C (en) | 2006-01-17 | 2006-01-17 | Flame-proof low-smoke low-toxicity epoxy adhesive |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100181835A CN100375772C (en) | 2006-01-17 | 2006-01-17 | Flame-proof low-smoke low-toxicity epoxy adhesive |
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| CN1800290A true CN1800290A (en) | 2006-07-12 |
| CN100375772C CN100375772C (en) | 2008-03-19 |
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ID=36810508
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101870801A (en) * | 2010-06-09 | 2010-10-27 | 舒城金泽信环保材料有限公司 | High-elasticity epoxy resin |
| CN101891949A (en) * | 2010-08-09 | 2010-11-24 | 常州天晟新材料股份有限公司 | Halogen free flame retardant liquid and method for preparing flame retardant sponge using same |
| CN102161875A (en) * | 2009-12-30 | 2011-08-24 | 第一毛织株式会社 | Attach film composition for semiconductor assembly, attach film for semiconductor assembly using the same and attach belt |
| CN102850986A (en) * | 2012-10-05 | 2013-01-02 | 王崇高 | Novel halogen-free flame retardant epoxy resin sealing glue |
| CN108753231A (en) * | 2018-06-27 | 2018-11-06 | 上海德联化工有限公司 | A kind of vehicle body polyamide modified epoxy resin structural adhesive and preparation method thereof |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0733500B2 (en) * | 1988-06-29 | 1995-04-12 | アイシン化工株式会社 | Difficult epoxy resin adhesive |
| JP2867277B2 (en) * | 1989-12-11 | 1999-03-08 | 旭化成工業株式会社 | Flame retardant adhesive composition |
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| CN102161875A (en) * | 2009-12-30 | 2011-08-24 | 第一毛织株式会社 | Attach film composition for semiconductor assembly, attach film for semiconductor assembly using the same and attach belt |
| CN101870801A (en) * | 2010-06-09 | 2010-10-27 | 舒城金泽信环保材料有限公司 | High-elasticity epoxy resin |
| CN101891949A (en) * | 2010-08-09 | 2010-11-24 | 常州天晟新材料股份有限公司 | Halogen free flame retardant liquid and method for preparing flame retardant sponge using same |
| CN102850986A (en) * | 2012-10-05 | 2013-01-02 | 王崇高 | Novel halogen-free flame retardant epoxy resin sealing glue |
| CN108753231A (en) * | 2018-06-27 | 2018-11-06 | 上海德联化工有限公司 | A kind of vehicle body polyamide modified epoxy resin structural adhesive and preparation method thereof |
| CN109970413A (en) * | 2019-04-10 | 2019-07-05 | 江苏霖生美家园艺有限公司 | A kind of gardens solid waste environmentally friendly binder and preparation method thereof |
| CN109970413B (en) * | 2019-04-10 | 2022-02-18 | 江苏霖生美家园艺有限公司 | Environment-friendly adhesive for garden solid waste and preparation method thereof |
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