CN102732201A - Wear-resistant and weather-resistant epoxy resin coating adhesive and its preparation method - Google Patents
Wear-resistant and weather-resistant epoxy resin coating adhesive and its preparation method Download PDFInfo
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Abstract
The invention which relates to a wear-resistant and weather-resistant epoxy resin coating adhesive and its preparation method belongs to the technical field of adhesives. The adhesive comprises a component A and a component B, wherein the component A comprises 6-16 parts of an alicyclic glycidyl ether epoxy resin, 15-25 parts of a novolac epoxy resin, 4-6 parts of an epoxy active diluent, 4-6 parts of a responsive flexibilizer, 0.5-1.2 parts of a coupling agent, 0.4-0.8 parts of organic bentonite, 0.3-0.5 parts of an antioxidant, 0.4-0.8 parts of an ultraviolet ray absorbent, 40-45 parts of white corundum powder, 3-5 parts of filler powder, 4-6 parts of a short glass fiber, 5 parts of a yellow color paste, and 1-2 parts of white carbon black; and the component B comprises 15-25 parts of an alicyclic amine, 10-15 parts of isophorone diamine, 6-9 parts of aminoethylpiperazine, 2-3 parts of a curing accelerator, 40-45 parts of the white corundum powder, 4-6 parts of the short glass fiber, 4-6 parts of the filler powder and 3-5 parts of the white carbon black. The preparation method comprises the steps of yellow color paste preparation, component A preparation and component B preparation. Compared with adhesives obtained through the prior art, the mechanical strength and the wear resistance of the adhesive of the invention are obviously improved.
Description
Technical field:
The present invention relates to a kind of wear-resistant, weathe resistance epoxy resin coating adhesive and preparation method thereof, belong to the adhesive technology field.
Technical background:
Epoxy resin has good adhesion to most materials, and the epoxy resin after the curing has the bonding strength height, thermotolerance, chemical resistant properties, characteristics such as dielectricity is good, shrinking percentage is low; Aspect bonding and protective coating, liquid dihydroxyphenyl propane Racemic glycidol ether type epoxy is used comparatively extensive, but because of it contains phenyl ring, its ultraviolet light resistant performance and ageing-resistant performance are relatively poor, and progressively variable color, efflorescence under the environment out of doors makes bonding and protection was lost efficacy.In addition, cohesion stress was big when the liquid bisphenol A epoxide resin solidified, and cured article is hard and crisp, and resistance to acids and bases, humidity resistance are relatively poor, prepare wear-resisting, weather-proof, shock proof protective coating with this and are limited in the use.And; Liquid bisphenol A epoxide resin viscosity is big (as: E-51 epoxy resin viscosity index is 10000-15000mpa.s); The prior art polygamy closes and uses epoxy resin diluent to prepare LV protective coating glue, though reduced viscosity, the cross-linking density of curing reaction also decreases; The performance of protective coating is reduced, and epoxide diluent have certain toxicity and emission problem more.
Use preparation such as low viscous heterocyclic epoxy resin, aliphatic epoxy resin protective coating, or cost is higher, or the ambient cure difficulty, lessly in outdoor protective coating, uses.
The cured article of line style phenolic aldehyde polyglycidyl ether type epoxy resin has higher cross-linking density, better heat-resisting property, weathering resistance and acid-alkali-corrosive-resisting property, but same hard and crisp, toughness is relatively poor, and viscosity is higher should not prepare the LV coating adhesive; Do not contain phenyl ring and hydroxyl in the cycloaliphatic epoxy resin molecular structure, thereby have UV resistant radiation preferably and weather resistance, and have lower viscosity; But its reactive behavior is lower, is difficult to react with common amine curing agent at normal temperatures, has also limited its application for this reason.
Summary of the invention:
The objective of the invention is to solve in the prior art technical problems such as epoxide resin protective coating abrasion performance, weather resisteant, loss of properties on aging and application property be bad; A kind of wear-resistant, weather resisteant epoxy coating glue and preparation method thereof is provided; Have LV, ambient cure, HS, high-wearing feature with this epoxy protective coating that obtains; And having toughness preferably, photostabilization, weathering resistance, ageing-resistant performance and thermal stability are good.
Another object of the present invention provides the preparation method of this wear-resistant, weather resisteant epoxy coating glue.
In order to achieve the above object, this wear-resistant, weather resisteant epoxy coating glue of the present invention be achieved in that by following epoxy resin component (hereinafter to be referred as: the A component) and curing agent component (hereinafter to be referred as: the B component) form:
A component: alicyclic tetraglycidel ether epoxy resin: 6-16 part, novolac epoxy: 15-25 part, epoxy active diluent: 4-6 part, reactive toughner 4-6 part; Coupling agent: 0.5-1.2 part; Organobentonite 0.4-0.8 part; Oxidation inhibitor: 0.3-0.5 part, UV light absorber 0.4-0.8 part, white alundum powder 40-45 part, filler powder: 3-5 part, short glass fiber 4-6 part, 5 parts of yellow colors, WHITE CARBON BLACK 1-2 part;
B component: aliphatic cyclic amine: 15-25 part, isophorone diamine: 10-15 part, aminoethyl piperazine: 6-9 part, curing catalyst: 2-3 part, white alundum powder: 40-45 part, short glass fiber: 4-6 part, filler powder: 4-6 part, WHITE CARBON BLACK: 3-5 part;
The weight ratio of epoxy resin component and curing agent component is: 100: 18～22.
Described novolac epoxy is characterized by line style phenolic aldehyde polyglycidyl ether, and epoxy equivalent (weight) is that 165-175g/eq, viscosity are the liquid phenolic epoxy resin of 9500-12000mPa.s, as: PNE172 etc.
It is the wherein a kind of of 0.45-0.55 that described alicyclic glycidyl ether is characterized by the saturated fat ring structure, the oxirane value that contain two epoxy group(ing), as: CER-170 etc.
Described reactive toughner, be meant have branched structure, the CYH-277 of many active end groups or solidify to divide the QS-BN of the elastic granule disperse phase that coordinates.
Described epoxide resin reactive diluent; Can be that oxirane value is 1 of 0.50～0.60eq/100g, the 2-cylohexanediol diglycidyl ether, as: (reference examples then is 1 to CD-1180; 6-hexanediol diglycidyl ether epoxide diluent, oxirane value 0.65～0.70eq/100g).
Described coupling agent is characterized in that referring to the commercially available silane coupling agent that contains epoxy functionality, as: γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560) or γ-methacryloxypropyl trimethoxy silane (KH570) wherein a kind of.
Described organobentonite is meant commercially available 200 order organobentonite dry powder through surface-active-treatment.
Described oxidation inhibitor is meant Hinered phenols 2, a kind of (antioxidant 1010) in 6-tri-tert-4-methylphenol (antioxidant 264) or four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
Said yellow color is meant 200 order coating medium chrome yellow medium yellow pigment is prefabricated into the alicyclic tetraglycidel ether epoxy resin color (use 5 parts of yellow colors among the present invention in the A component, promptly contain 4 parts of cycloaliphatic epoxy resins and 1 part of coating medium chrome yellow medium yellow pigment) that contains coating medium chrome yellow medium yellow 20% before use earlier.
Described UV light absorber is meant benzotriazole category, as: 2-(2 '-hydroxyl-3 ', 5 '-two uncle's phenyl)-5-chlorination benzotriazole, as: UV327.
Described aliphatic cyclic amine can be that the reactive hydrogen equivalent is the hydrogenation m-xylene diamine (H-MXDA) of 35.5g/Eq or to have an identical reactive hydrogen normal 1, and two (aminomethyl) hexanaphthenes of 4-(1,4-BAC).
Described isophorone diamine be meant the reactive hydrogen equivalent be 42.6g/Eq aliphatic cyclic amine.
Described aminoethyl piperazine is meant that the reactive hydrogen equivalent is the aliphatic cyclic amine (N-AEP) of 15g/Eq.
Described curing catalyst is a tertiary amines promotor 2,4, and the 6-tri(dimethylaminomethyl)phenol is like DMP-30.
Described white alundum powder is commercially available abrasive material level 1000# white alundum powder with trigonal system.
Described filler powder is meant 1000 orders calcining α-AL
2O
3Powder or 3000 order calcined kaolins, its common trait are that powder surface is through the active processing of coupling agent, good dispersion in resin and curing component.
Described short glass fiber is meant fine footpath at 8-12um, and length is less than the short glass fiber powder of 0.5mm.
Described WHITE CARBON BLACK is meant that specific surface area is 200M
2The fumed silica of/g.
The present invention is wear-resistant, the preparation method of weathe resistance epoxy resin coating adhesive, is divided into: yellow color preparation method, A method for preparing ingredients thereof and B method for preparing ingredients thereof:
Yellow color preparation:
Take by weighing alicyclic tetraglycidel ether epoxy resin, coating medium chrome yellow medium yellow pigment, mix wetting with scoop; Roller is crossed three times with compound in adjustment three-roll grinder rod gap, gets yellow color.
The preparation of A component:
Novolac epoxy, alicyclic tetraglycidel ether epoxy resin, reactive toughner are placed planetary dispersion machine, be heated to 70 ℃ of glue temperatures, added epoxide resin reactive diluent, organobentonite dispersed with stirring 30 minutes; Add filler powder, the dispersion of white alundum powder high-speed stirring 30 minutes; Add short glass fiber, dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control, and adding coupling agent, oxidation inhibitor, uv-absorbing agent stirred 15 minutes, added yellow color, WHITE CARBON BLACK, and high-speed stirring was disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging.
The preparation of B component:
Aliphatic cyclic amine, isophorone diamine, aminoethyl piperazine, curing catalyst are placed planetary dispersion machine, dispersed with stirring 10 minutes; Add organobentonite, dispersed with stirring 30 minutes; 50 ℃ of temperature controls add filler powder, white alundum powder, dispersed with stirring 20 minutes; Add short glass fiber, dispersed with stirring 10 minutes; Add WHITE CARBON BLACK, dispersed with stirring 20 minutes vacuumizes and stirring at low speed 30 minutes, filters discharging.
The use of tackiness agent: use electric blender, the A component was stirred 3 minutes, the weight ratio by 100: 18～22 takes by weighing A, B component, stirs 5 minutes (or with scoop mixing) with electric blender, leaves standstill 5 minutes; The glue that mixes is placed applying glue face, scrape floating putting in order with the notched scraper that is suitable for coat-thickness, ambient cure is more than 24 hours.
The present invention is wear-resistant, compared with present technology the weathe resistance epoxy resin coating adhesive has distinguishing feature and substantive progress:
1, adopt the linear novolac glycidyl ethers epoxy resin with 2 above epoxy group(ing), normal temperature descends and amine curing agent has than high reaction activity, has higher cross-linking density after the curing, and than high glass transition temperature, acid and alkali-resistance and aqueous corrosion property are good, and bonding strength is high.
2, adopt alicyclic tetraglycidel ether epoxy resin, do not contain phenyl ring, be the saturated fat ring structure, thereby its cured article ultraviolet resistance radiation, good weatherability, can long-term outdoor use; Molecular structure ether-containing key isopolarity key and hydroxyl etc., thereby have good cementability and physical strength; LV (＜100mpa.s&25 ℃) has epoxy resin diluent concurrently and uses, and ambient temperature curable has good weathering resistance, thermotolerance and ageing-resistant performance after the curing.
3, adopt cylohexanediol diglycidyl ether as thinner, have than highly diluted property and better reactive behavior its cured product photostabilization, weather resisteant excellence, and the discharging of low toxicity VOC free.
4, adopt reactive toughner, utilize the intramolecule hole to cause cured article to produce shear deformation and the dissipation impact energy, or utilize the sea-island effect attenuate shock energy that solidifies the phase-splitting generation, effectively improve cured article toughness and coating resistance to impact shock.
5, the chrome yellow that adopts coating to handle, the photostabilization of raising colored film.
6, adopt 1000 order white alundum powders,, when guaranteeing good dispersion, take into account resistance to sinking, guarantee abrasion property as the abrasive aggregates of coating.
7, adopt Hinered phenols antioxidant, catch the radical that degraded produces; Adopt the special-purpose uv-absorbing agent of resin, transform the UV energy, heat-resisting distillation improves the coating thermo-oxidative stability, reduces photodegradation, improves anti-ultraviolet radiation, ageing-resistant, the anti-yellowing property of protective coating system.
8, adopt short glass fiber, guarantee coating higher draw tensile strength and shearing impact intensity.
9, adopt suspension thixotropic agent organobentonite and WHITE CARBON BLACK, guarantee the good dispersiveness of tackiness agent, anti-heavy property, the thixotropy and the sag prevention performance of appropriateness.
10, adopt the alicyclic ring amine curing agent with greater activity, the low cycloaliphatic epoxy resin of activity of curing reaction at normal temperatures; Solidify back film forming light, hard, ultraviolet light resistant, good weatherability have than high-adhesive-strength, shock resistance and wear resistance, corrosion-resistant outstanding, and second-order transition temperature is high.
11, do not need complex apparatus, preparation technology is simple.
12, easy to use, better suited working life and good workability.
Wear-resistant, the weathe resistance epoxy resin coating adhesive of the present invention's preparation; Compared with prior art, the physical strength and the wear resisting property of wear Protection coating are significantly improved, and shearing resistance reaches 27.5MPa; The body tensile strength reaches 72.6MPa, and second-order transition temperature (Tg) reaches 118.6 ℃; In weather artificial accelerated aging test of control group UV-light and relative wear resistance, the present invention tests exemplar and has significant advantage.
Embodiment
Below in conjunction with embodiment and reference examples essence of the present invention and characteristic are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1:
Yellow color preparation: take by weighing alicyclic tetraglycidel ether epoxy resin CER-170 800g, coating medium chrome yellow medium yellow pigment 200g, mix wetting with scoop; Roller is crossed three times with compound in adjustment three-roll grinder rod gap, gets yellow color.
The preparation of A component:
Take by weighing novolac epoxy PNE-172250g, alicyclic tetraglycidel ether epoxy resin CER-17060g, epoxy resin toughener CYH-27750g; Join in the planetary dispersion machine of 2L, be heated to 70 ℃ of glue temperatures while stirring, middling speed stirred 15 minutes; Add epoxide diluent 1; 2-hexanediol diglycidyl ether CD-118050g adds organobentonite 4g, dispersed with stirring 30 minutes; Add the active kaolin 50g that handles of 3000 orders; Add 1000 order white alundum powder 400g, high-speed stirring was disperseed 30 minutes; Add short glass fiber 50g, middling speed dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control, adds coupling agent KH560 10g, oxidation inhibitor 3g, uv-absorbing agent 5g, and middling speed stirred 15 minutes; Add yellow color 50g (containing 40gCER-170, as follows), WHITE CARBON BLACK 18g, high-speed stirring was disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take by weighing aliphatic cyclic amine 200g in proportion, isophorone diamine 150g, aminoethyl piperazine 90g, 2,4,6-tri(dimethylaminomethyl)phenol 20g, organobentonite 6g place 2L duplicate rows star dynamic mixing still, and middling speed stirred 30 minutes; Add 3000 order kaolin 44g, 1000 order white fused alumina 400g, high-speed stirring 15 minutes; Add short glass fiber 50g, middling speed stirred 10 minutes, added WHITE CARBON BLACK 40g, high-speed stirring 20 hours; Vacuumize and stirring at low speed 30 minutes discharging (total amount 1Kg);
The use of tackiness agent:
Use electric blender that the A component was stirred 3 minutes, the ratio that takes by weighing in proportion in 100: 18 takes by weighing A, B component, and stirrer mixes 5 minutes (or mix with scoop); The applying glue face of placing; Select the notched scraper of corresponding specification for use according to coat-thickness, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 2:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take by weighing novolac epoxy PNE-172 200g, alicyclic tetraglycidel ether epoxy resin CER-170120g, epoxy resin toughener CYH-277 40g; Join in the planetary dispersion machine of 2L, be heated to 70 ℃ of glue temperatures while stirring, middling speed stirred 15 minutes; Add epoxide diluent 1; 2-hexanediol diglycidyl ether CD-1180 40g adds organobentonite 6g, dispersed with stirring 30 minutes; Add the active kaolin 30g that handles of 3000 orders; Add 1000 order white alundum powder 439g, high-speed stirring was disperseed 30 minutes; Add short glass fiber 40g, middling speed dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control, adds coupling agent KH560 12g, oxidation inhibitor 4g, uv-absorbing agent 4g, and middling speed stirred 15 minutes; Add yellow color 50g, WHITE CARBON BLACK 15g, high-speed stirring was disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take by weighing aliphatic cyclic amine 250g in proportion, isophorone diamine 100g, aminoethyl piperazine 60g, 2,4,6-tri(dimethylaminomethyl)phenol 26g, organobentonite 4g place 2L duplicate rows star dynamic mixing still, and middling speed stirred 30 minutes; Add 3000 order kaolin 40g, 1000 order white fused alumina 420g, high-speed stirring 15 minutes; Add short glass fiber 50g, middling speed stirred 10 minutes, added WHITE CARBON BLACK 50g, high-speed stirring 20 hours; Vacuumize and stirring at low speed 30 minutes discharging (total amount 1Kg);
The use of tackiness agent:
Use electric blender that the A component was stirred 3 minutes, the ratio that takes by weighing in proportion in 100: 21 takes by weighing A, B component, and stirrer mixes 5 minutes (or mix with scoop); The applying glue face of placing; Select the notched scraper of corresponding specification for use according to coat-thickness, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 3:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take by weighing novolac epoxy PNE-172 150g, alicyclic tetraglycidel ether epoxy resin CER-170160g, epoxy resin toughener QS-BN40g; Join in the planetary dispersion machine of 2L, be heated to 70 ℃ of glue temperatures while stirring, middling speed stirred 15 minutes; Add epoxide diluent 1; 2-hexanediol diglycidyl ether CD-1180 40g adds organobentonite 8g, dispersed with stirring 30 minutes; Add the active kaolin 50g that handles of 3000 orders; Add 1000 order white alundum powder 418g, high-speed stirring was disperseed 30 minutes; Add short glass fiber 60g, middling speed dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control, adds coupling agent KH560 5g, oxidation inhibitor 3g, uv-absorbing agent 6g, and middling speed stirred 15 minutes; Add yellow color 50g, WHITE CARBON BLACK 10g, high-speed stirring was disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take by weighing aliphatic cyclic amine 240g in proportion, isophorone diamine 100g, aminoethyl piperazine 90g, 2,4,6-tri(dimethylaminomethyl)phenol 30g, organobentonite 5g place 2L duplicate rows star dynamic mixing still, and middling speed stirred 30 minutes; Add 3000 order kaolin 40g, 1000 order white fused alumina 405g, high-speed stirring 15 minutes; Add short glass fiber 40g, middling speed stirred 10 minutes, added WHITE CARBON BLACK 50g, high-speed stirring 20 hours; Vacuumize and stirring at low speed 30 minutes discharging (total amount 1Kg);
The use of tackiness agent:
Use electric blender that the A component was stirred 3 minutes, the ratio that takes by weighing in proportion in 100: 22 takes by weighing A, B component, and stirrer mixes 5 minutes (or mix with scoop); The applying glue face of placing; Select the notched scraper of corresponding specification for use according to coat-thickness, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 4:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take by weighing novolac epoxy PNE-172 180g, alicyclic tetraglycidel ether epoxy resin CER-170103g, epoxy resin toughener CYH-277 60g; Join in the planetary dispersion machine of 2L, be heated to 70 ℃ of glue temperatures while stirring, middling speed stirred 15 minutes; Add epoxide diluent 1; 2-hexanediol diglycidyl ether CD-1180 50g adds organobentonite 8g, dispersed with stirring 30 minutes; Add the active kaolin 30g that handles of 3000 orders; Add 1000 order white alundum powder 450g, high-speed stirring was disperseed 30 minutes; Add short glass fiber 40g, middling speed dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control, adds coupling agent KH560 7g, oxidation inhibitor 6g, uv-absorbing agent 8g, and middling speed stirred 15 minutes; Add yellow color 50g, WHITE CARBON BLACK 10g, high-speed stirring was disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take by weighing aliphatic cyclic amine 214g in proportion, isophorone diamine 125g, aminoethyl piperazine 70g, 2,4,6-tri(dimethylaminomethyl)phenol 25g, organobentonite 6g place 2L duplicate rows star dynamic mixing still, and middling speed stirred 30 minutes; Add 3000 order kaolin 40g, 1000 order white fused alumina 450g, high-speed stirring 15 minutes; Add short glass fiber 40g, middling speed stirred 10 minutes, added WHITE CARBON BLACK 30g, high-speed stirring 20 hours; Vacuumize and stirring at low speed 30 minutes discharging (total amount 1Kg);
The use of tackiness agent:
Use electric blender that the A component was stirred 3 minutes, the ratio that takes by weighing in proportion in 100: 20 takes by weighing A, B component, and stirrer mixes 5 minutes (or mix with scoop); The applying glue face of placing; Select the notched scraper of corresponding specification for use according to coat-thickness, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 5:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take by weighing novolac epoxy PNE-172 210g, alicyclic tetraglycidel ether epoxy resin CER-17080g, epoxy resin toughener QS-BN60g; Join in the planetary dispersion machine of 2L, be heated to 70 ℃ of glue temperatures while stirring, middling speed stirred 15 minutes; Add epoxide diluent 1; 2-hexanediol diglycidyl ether CD-1180 60g adds organobentonite 7g, dispersed with stirring 30 minutes; Add the active kaolin 35g that handles of 3000 orders; Add 1000 order white alundum powder 420g, high-speed stirring was disperseed 30 minutes; Add short glass fiber 50g, middling speed dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control, adds coupling agent KH560 8g, oxidation inhibitor 4g, uv-absorbing agent 6g, and middling speed stirred 15 minutes; Add yellow color 50g, WHITE CARBON BLACK 20g, high-speed stirring was disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take by weighing aliphatic cyclic amine 220g in proportion, isophorone diamine 120g, aminoethyl piperazine 75g, 2,4,6-tri(dimethylaminomethyl)phenol 21g, organobentonite 6g place 2L duplicate rows star dynamic mixing still, and middling speed stirred 30 minutes; Add 3000 order kaolin 60g, 1000 order white fused alumina 400g, high-speed stirring 15 minutes; Add short glass fiber 60g, middling speed stirred 10 minutes, added WHITE CARBON BLACK 40g, high-speed stirring 20 hours; Vacuumize and stirring at low speed 30 minutes discharging (total amount 1Kg);
The use of tackiness agent:
Use electric blender that the A component was stirred 3 minutes, the ratio that takes by weighing in proportion in 100: 19 takes by weighing A, B component, and stirrer mixes 5 minutes (or mix with scoop); The applying glue face of placing; Select the notched scraper of corresponding specification for use according to coat-thickness, scrape floating wholely, self-vulcanizing is more than 24 hours.
The comparative example:
Yellow color preparation: take by weighing bisphenol A epoxide resin E-51 800g, coating medium chrome yellow medium yellow pigment 200g, mix wetting with scoop; Roller is crossed three times with compound in adjustment three-roll grinder rod gap, gets yellow color.
The preparation of A component:
Take by weighing bisphenol A epoxide resin E-51 320g, epoxy resin toughener QS-BN50g joins in the planetary dispersion machine of 2L; Be heated to 70 ℃ of glue temperatures while stirring; Middling speed stirred 15 minutes, added epoxide diluent 1,6 hexanediol diglycidyl ether 50g; Add organobentonite 5g, dispersed with stirring 30 minutes; Add the active kaolin 37g that handles of 3000 orders; Add 1000 order white alundum powder 450g, high-speed stirring was disperseed 30 minutes; Add short glass fiber 60g, middling speed dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control, adds coupling agent KH560 10g, oxidation inhibitor 3g, uv-absorbing agent 5g, and middling speed stirred 15 minutes; Add yellow color 50g (containing E-51 epoxy resin 40g), WHITE CARBON BLACK 10g, high-speed stirring was disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
(with the preparation of embodiment 4B component)
The use of tackiness agent:
Use electric blender that the A component was stirred 3 minutes, the ratio that takes by weighing in proportion in 100: 20 takes by weighing A, B component, and stirrer mixes 5 minutes (or mix with scoop); The applying glue face of placing; Select the notched scraper of corresponding specification for use according to coat-thickness, scrape floating wholely, self-vulcanizing is more than 24 hours.
Wear-resistant, Weather-resistant epoxy coating adhesive and comparative example that the foregoing description 1-5 is made carry out measuring mechanical property, relative wear rate test, glass transition temperature test and the test of ultraviolet artificial accelerated aging, data such as table one, table two, table three by the tackiness agent touchstone.
1, table 1 is seen in embodiment and comparative example's measuring mechanical property contrast
Table 1
Annotate *: be 45# steel-45# steel sandblast test piece.
Annotate * *: body cast exemplar ambient cure 168 hours
2, table 2 is seen in the contrast of embodiment and comparative example's cut resistance test and glass transition temperature (Tg)
Table 2
Annotate *: adopt cast oar type test specimen, 60%30# silit-water, 200 rev/mins are continuous 72 hours.
3, embodiment and comparative example press GB/T14522-93 UV-light weather artificial accelerated aging test contrast, see table 3
Table 3
Annotate *: adopt the fluorescent ultraviolet lamp proofing box, 313nmUVB, 50-60 ℃ of condensation-illumination respectively is 4 hours periods.
Contrast through the foregoing description and reference examples test, testing data, embodiment has over-all properties significantly, particularly after the ultraviolet artificial accelerated aging test; The embodiment exemplar still has tensile strength preferably; And the reference examples exemplar, outward appearance has presented albefaction, efflorescence, and the mechanical property decay is serious.
The present invention adopts novolac epoxy resin, cycloaliphatic epoxy resin, cylohexanediol diglycidyl ether diluent combined, adopts the higher alicyclic ring amine curing agent combination of reactive behavior, and the epoxy coat glue that makes is had: LV, workability are good; Ambient cure has higher adhesiveproperties and physical strength after the curing; Phenolic aldehyde epoxy, cycloaliphatic epoxy resin and aliphatic cyclic amine curing system provide higher cross-linking density, make coating have wear resistance and shock resistance preferably; Especially wear-resistant, the weathe resistance epoxy resin coating adhesive of the present invention has comparatively outstanding ultraviolet light resistant and weather resistance, and markings, protective coating application facet have remarkable and substantial characteristics out of doors.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. wear-resistant, a weathe resistance epoxy resin coating adhesive is processed by epoxy resin ingredient that is referred to as the A component and the curing agent component that is referred to as the B component, and the weight ratio of A component and B component is 100: 18～22, it is characterized in that:
Described A component comprise weight part for 6-16 part alicyclic tetraglycidel ether epoxy resin, the novolac epoxy of 15-25 part, the epoxy active diluent of 4-6 part, the reactive toughner of 4-6 part, the coupling agent of 0.5-1.2 part, the organobentonite of 0.4-0.8 part, the oxidation inhibitor of 0.3-0.5 part, the UV light absorber of 0.4-0.8 part, the white alundum powder of 40-45 part, the filler powder of 3-5 part, the short glass fiber of 4-6 part, 5 parts yellow color and the WHITE CARBON BLACK of 1-2 part;
Described B component comprises that weight part is the aliphatic cyclic amine of 15-25 part, the isophorone diamine of 10-15 part, the aminoethyl piperazine of 6-9 part, the curing catalyst of 2-3 part, the white alundum powder of 40-45 part, the short glass fiber of 4-6 part, the filler powder of 4-6 part and the WHITE CARBON BLACK of 3-5 part.
2. a kind of wear-resistant, weathe resistance epoxy resin coating adhesive according to claim 1 is characterized in that described alicyclic glycidyl ether is to contain wherein a kind of of the saturated fat ring structure of two epoxy group(ing) and alicyclic glycidyl ether that oxirane value is 0.45-0.55; Described novolac epoxy is that line style phenolic aldehyde polyglycidyl ether and epoxy equivalent (weight) are the liquid phenolic epoxy resin of 165-175g/eq; Described epoxide resin reactive diluent is that oxirane value is 1 of 0.50～0.60eq/100g, the 2-cylohexanediol diglycidyl ether; Described reactive toughner be meant have branched structure, epoxide resin reactive toughner many active end groups flexibility compound or that solidify to divide the elastic granule disperse phase that coordinates; Described coupling agent is the silane coupling agent that contains epoxy functionality, comprises γ-glycidyl ether oxygen propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane; Described organobentonite is 200 order organobentonite dry powder through surface-active-treatment; Described oxidation inhibitor is Hinered phenols 2,6-tri-tert-4-methylphenol or four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester; 5 parts of yellow colors were meant by 4 parts of cycloaliphatic epoxy resins and 1 part of prefabricated forming of coating medium chrome yellow medium yellow pigment during described A component was formed; Described UV light absorber is the UV light absorber of benzotriazole category, comprises 2-(2 '-hydroxyl-3 ', 5 '-two uncle's phenyl)-5-chlorination benzotriazole.
3. a kind of wear-resistant, weathe resistance epoxy resin protective coating glue according to claim 1; It is characterized in that described aliphatic cyclic amine is that hydrogenation m-xylene diamine or the reactive hydrogen equivalent of 35.5g/Eq is 1 of 35.5g/Eq for the reactive hydrogen equivalent, two (aminomethyl) hexanaphthenes of 4-; Described isophorone diamine be meant the reactive hydrogen equivalent be 42.6g/Eq aliphatic cyclic amine; Described aminoethyl piperazine is meant that the reactive hydrogen equivalent is the aliphatic cyclic amine of 15g/Eq; Described curing catalyst is a tertiary amines promotor 2,4, the 6-tri(dimethylaminomethyl)phenol; Described white alundum powder is commercially available abrasive material level 1000# white alundum powder with trigonal system; Described filler powder be meant powder surface through coupling agent active handle, finely disseminated 1000 orders calcining α-AL in resin and curing component
20
3Powder or 3000 order calcined kaolins; Described short glass fiber is meant that fine footpath is at 8-12um, the length short glass fiber powder less than 0.5mm; Described WHITE CARBON BLACK is meant that specific surface area is 200M
2The fumed silica of/g.
4. prepare the method for described a kind of wear-resistant, the weathe resistance epoxy resin protective coating glue of claim 1, comprise yellow color preparation method, A method for preparing ingredients thereof and B method for preparing ingredients thereof:
Yellow color preparation method comprises:
1) takes by weighing alicyclic tetraglycidel ether epoxy resin, coating medium chrome yellow medium yellow pigment, mix wetting with scoop;
2) roller is crossed three times with compound in adjustment three-roll grinder rod gap, gets yellow color.
The A method for preparing ingredients thereof comprises:
1) novolac epoxy, alicyclic tetraglycidel ether epoxy resin, reactive toughner are placed planetary dispersion machine, be heated to 70 ℃ of glue temperatures;
2) added epoxide resin reactive diluent, organobentonite dispersed with stirring 30 minutes;
3) add filler powder, the dispersion of white alundum powder high-speed stirring 30 minutes;
4) add short glass fiber, dispersed with stirring 10 minutes is cooled to 40 ℃ and temperature control;
5) adding coupling agent, oxidation inhibitor, uv-absorbing agent stirred 15 minutes;
6) add yellow color, WHITE CARBON BLACK, high-speed stirring was disperseed 20 minutes;
7) vacuumize and stirring at low speed 30 minutes;
8) filtration, discharging;
The B method for preparing ingredients thereof comprises:
1) aliphatic cyclic amine, isophorone diamine, aminoethyl piperazine, curing catalyst are placed planetary dispersion machine, dispersed with stirring 10 minutes;
2) add organobentonite, dispersed with stirring 30 minutes;
3) temperature control is 50 ℃, adds filler powder, white alundum powder, dispersed with stirring 20 minutes;
4) add short glass fiber, dispersed with stirring 10 minutes;
5) add WHITE CARBON BLACK, dispersed with stirring 20 minutes vacuumizes and stirring at low speed 30 minutes;
6) filter discharging.
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