CN102732201B - 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 adhesive technology field.
Technical background:
Epoxy resin has good adhesion to most materials, and it is high that the epoxy resin after solidifying has bonding strength, thermotolerance, chemical resistant properties, the feature such as dielectricity is good, shrinking percentage is low; Aspect bonding and protective coating, the application of liquid dihydroxyphenyl propane Racemic glycidol ether type epoxy is comparatively extensive, but because it contains phenyl ring, its ultraviolet light resistant performance and ageing-resistant performance are poor, and progressively variable color of meeting, efflorescence under environment out of doors makes bonding and protection inefficacy.In addition, when liquid bisphenol A epoxide resin solidifies, cohesion stress is large, and cured article is hard and crisp, and resistance to acids and bases, humidity resistance are poor, prepare wear-resisting, weather-proof, shock proof protective coating limited in the use with this.And, liquid bisphenol A epoxide resin viscosity is large (as: E-51 epoxy resin viscosity index is 10000-15000mpa.s), prior art is used in conjunction with epoxy resin diluent more and prepares low viscosity protective coating glue, although reduced viscosity, but 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 low viscous heterocyclic epoxy resin, aliphatic epoxy resin etc. to prepare protective coating, or cost is higher, or 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, preferably thermotolerance, weathering resistance and acid-alkali-corrosive-resisting, but same hard and crisp, toughness is poor, and viscosity is higher should not prepare low viscosity coating adhesive; In cycloaliphatic epoxy resin molecular structure, do not contain phenyl ring and hydroxyl, thereby there is good UV resistant radiation and weather resistance, and there is lower viscosity; But its reactive behavior is lower, be difficult to react with common amine curing agent at normal temperatures, also limited its application for this reason.
Summary of the invention:
The object of the invention is to solve in prior art the 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, the epoxy protective coating obtaining with this has low viscosity, ambient cure, high strength, high-wearing feature, and thering is good toughness, photostabilization, weathering resistance, ageing-resistant performance and thermal stability are good.
Another object of the present invention is to provide 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: A component) and curing agent component (hereinafter to be referred as: 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 toughening agent 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 the liquid phenolic epoxy resin that 165-175g/eq, viscosity are 9500-12000mPa.s, as: PNE172 etc.
Described alicyclic glycidyl ether is characterized by the saturated fat ring structure, the oxirane value that contain two epoxy group(ing), and to be 0.45-0.55 wherein a kind of, as: CER-170 etc.
Described reactive toughening agent, refer to there is branched structure, the CYH-277 of many active end groups or solidify the QS-BN of the elastic granule disperse phase that minute coordinates.
Described epoxide resin reactive diluent, can be that oxirane value is 1 of 0.50～0.60eq/100g, 2-cylohexanediol diglycidyl ether, as: (reference examples is 1 to CD-1180,6-hexanediol diglycidyl ether epoxide diluent, oxirane value 0.65～0.70eq/100g).
Described coupling agent, it 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 refers to the commercially available 200 order organobentonite dry powder through surface-active-treatment.
Described oxidation inhibitor refers to Hinered phenols 2, a kind of (antioxidant 1010) in 6-tri-tert-4-methylphenol (antioxidant 264) or four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
Described yellow color refers to 200 order coating middle chrome pigments is first prefabricated into the alicyclic tetraglycidel ether epoxy resin color (use 5 parts of yellow colors in the present invention in A component, contain 4 parts of cycloaliphatic epoxy resins and 1 part of coating middle chrome pigment) containing coating medium chrome yellow medium yellow 20% before use.
Described UV light absorber refers to benzotriazole category, as: 2-(2 '-hydroxyl-3 ', 5 '-bis-tertiary phenyl)-5-chlorination benzotriazole, as: UV327.
Described aliphatic cyclic amine can be that reactive hydrogen equivalent is the hydrogenation m-xylene diamine (H-MXDA) of 35.5g/Eq or Isosorbide-5-Nitrae-bis-(aminomethyl) hexanaphthene (Isosorbide-5-Nitrae-BAC) with identical reactive hydrogen equivalent.
Described isophorone diamine refer to reactive hydrogen equivalent be 42.6g/Eq aliphatic cyclic amine.
Described aminoethyl piperazine refers to that reactive hydrogen equivalent is the aliphatic cyclic amine (N-AEP) of 15g/Eq.
Described curing catalyst is tertiary amines promotor 2,4, and 6-tri(dimethylaminomethyl)phenol, as DMP-30.
Described white alundum powder is the commercially available abrasive material level 1000# white alundum powder with trigonal system.
Described filler powder refers to 1000 order calcining α-AL
2o
3powder or 3000 order calcined kaolins, its common trait is that powder surface is through the active processing of coupling agent, good dispersion in resin and curing component.
Described short glass fiber refers to that fine footpath is at 8-12um, and length is less than the short glass fiber powder of 0.5mm.
Described white carbon black, refers to 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 alicyclic tetraglycidel ether epoxy resin, coating middle chrome pigment, with scoop, mix wetting; Adjust three-roll grinder rod gap, compound is crossed to roller three times, obtain yellow color.
The preparation of A component:
Novolac epoxy, alicyclic tetraglycidel ether epoxy resin, reactive toughening agent are placed in to planetary dispersion machine, are heated to 70 ℃ of glue temperatures, add epoxide resin reactive diluent, organobentonite dispersed with stirring 30 minutes; Add filler powder, white alundum powder high-speed stirring to disperse 30 minutes; Add short glass fiber, dispersed with stirring 10 minutes, is cooled to 40 ℃ and temperature control, adds coupling agent, oxidation inhibitor, uv-absorbing agent to stir 15 minutes, adds yellow color, white carbon black, and high-speed stirring is 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 in to 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, A component is stirred 3 minutes, the weight ratio by 100: 18～22 takes A, B component, stirs 5 minutes (or mixing with scoop), standing 5 minutes with electric blender; The glue mixing is placed in to applying glue face, to be suitable for the notched scraper of coat-thickness, scrapes floating wholely, ambient cure is more than 24 hours.
The present invention is wear-resistant, compared with the prior art 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), under normal temperature, have compared with high reaction activity with amine curing agent, after solidifying, have higher cross-linking density, compared with high glass transition temperature, acid and alkali-resistance and aqueous corrosion are good, and bonding strength is high.
2, adopting alicyclic tetraglycidel ether epoxy resin, containing phenyl ring, is 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 there is good cementability and physical strength; Low viscosity (25 ℃ of < 100mpa.s &), has epoxy resin diluent concurrently and uses, and ambient temperature curable has good weathering resistance, thermotolerance and ageing-resistant performance after solidifying.
3, adopt cylohexanediol diglycidyl ether as thinner, there is compared with highly diluted and better reactive behavior its cured product photostabilization, weather resisteant excellence, and the discharge of low toxicity VOC free.
4, adopt reactive toughening agent, utilize intramolecule hole to cause cured article to produce shear deformation and dissipation impact energy, or utilize the sea-island effect attenuate shock energy that solidifies phase-splitting generation, effectively improve cured article toughness and coating resistance to impact shock.
5, the chrome yellow that adopts coating to process, the photostabilization of raising colored film.
6, adopt 1000 order white alundum powders, as the abrasive aggregates of coating, when guaranteeing good dispersion, take into account resistance to sinking, guarantee the wear resistance of coating.
7, adopt Hinered phenols antioxidant, catch the free radical that degraded produces; Adopt the special-purpose uv-absorbing agent of resin, transform UV energy, heat-resisting distillation, improves 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 higher tensile strength and the shearing impact intensity of coating.
9, adopt suspension thixotropic agent organobentonite and white carbon black, guarantee good dispersiveness, the anti-settling property of tackiness agent, thixotropy and the sag prevention performance of appropriateness.
10, adopt the alicyclic ring amine curing agent with greater activity, the at normal temperatures low cycloaliphatic epoxy resin of activity of curing reaction; Film forming light, hard after solidifying, ultraviolet light resistant, good weatherability, have compared with high-adhesive-strength, shock resistance and wear resistance, corrosion-resistant outstanding, 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, weathe resistance epoxy resin coating adhesive prepared by the present invention, compared with prior art, physical strength and the wear resisting property of wear Protection coating are significantly improved, and shearing resistance reaches 27.5MPa, body tensile strength reaches 72.6MPa, and second-order transition temperature (Tg) reaches 118.6 ℃; In the artificial accelerated aging test of control group ultraviolet light weather resistance 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 feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1:
Yellow color preparation: take alicyclic tetraglycidel ether epoxy resin CER-170 800g, coating middle chrome pigment 200g, mix wetting with scoop; Adjust three-roll grinder rod gap, compound is crossed to roller three times, obtain yellow color.
The preparation of A component:
Take 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 while stirring 70 ℃ of glue temperatures, middling speed stirs 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 processes of 3000 orders; Add 1000 order white alundum powder 400g, high-speed stirring is 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 stirs 15 minutes; Add yellow color 50g (containing 40gCER-170, as follows), white carbon black 18g, high-speed stirring is disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take in proportion aliphatic cyclic amine 200g, isophorone diamine 150g, aminoethyl piperazine 90g, 2,4,6-tri(dimethylaminomethyl)phenol 20g, organobentonite 6g, be placed in 2L double-planet dynamic mixing still, and middling speed stirs 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 stirs 10 minutes, adds 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 A component is stirred 3 minutes, the ratio taking in proportion in 100: 18 takes A, B component, stirrer mixes 5 minutes (or mixing with scoop), the applying glue face of being placed in, according to coat-thickness, select the notched scraper of dimension, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 2:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take 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 while stirring 70 ℃ of glue temperatures, middling speed stirs 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 processes of 3000 orders; Add 1000 order white alundum powder 439g, high-speed stirring is 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 stirs 15 minutes; Add yellow color 50g, white carbon black 15g, high-speed stirring is disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take in proportion aliphatic cyclic amine 250g, isophorone diamine 100g, aminoethyl piperazine 60g, 2,4,6-tri(dimethylaminomethyl)phenol 26g, organobentonite 4g, be placed in 2L double-planet dynamic mixing still, and middling speed stirs 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 stirs 10 minutes, adds 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 A component is stirred 3 minutes, the ratio taking in proportion in 100: 21 takes A, B component, stirrer mixes 5 minutes (or mixing with scoop), the applying glue face of being placed in, according to coat-thickness, select the notched scraper of dimension, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 3:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take 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 while stirring 70 ℃ of glue temperatures, middling speed stirs 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 processes of 3000 orders; Add 1000 order white alundum powder 418g, high-speed stirring is 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 stirs 15 minutes; Add yellow color 50g, white carbon black 10g, high-speed stirring is disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take in proportion aliphatic cyclic amine 240g, isophorone diamine 100g, aminoethyl piperazine 90g, 2,4,6-tri(dimethylaminomethyl)phenol 30g, organobentonite 5g, be placed in 2L double-planet dynamic mixing still, and middling speed stirs 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 stirs 10 minutes, adds 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 A component is stirred 3 minutes, the ratio taking in proportion in 100: 22 takes A, B component, stirrer mixes 5 minutes (or mixing with scoop), the applying glue face of being placed in, according to coat-thickness, select the notched scraper of dimension, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 4:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take 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 while stirring 70 ℃ of glue temperatures, middling speed stirs 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 processes of 3000 orders; Add 1000 order white alundum powder 450g, high-speed stirring is 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 stirs 15 minutes; Add yellow color 50g, white carbon black 10g, high-speed stirring is disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take in proportion aliphatic cyclic amine 214g, isophorone diamine 125g, aminoethyl piperazine 70g, 2,4,6-tri(dimethylaminomethyl)phenol 25g, organobentonite 6g, be placed in 2L double-planet dynamic mixing still, and middling speed stirs 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 stirs 10 minutes, adds 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 A component is stirred 3 minutes, the ratio taking in proportion in 100: 20 takes A, B component, stirrer mixes 5 minutes (or mixing with scoop), the applying glue face of being placed in, according to coat-thickness, select the notched scraper of dimension, scrape floating wholely, self-vulcanizing is more than 24 hours.
Embodiment 5:
Yellow color preparation: (with embodiment 1)
The preparation of A component:
Take 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 while stirring 70 ℃ of glue temperatures, middling speed stirs 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 processes of 3000 orders; Add 1000 order white alundum powder 420g, high-speed stirring is 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 stirs 15 minutes; Add yellow color 50g, white carbon black 20g, high-speed stirring is disperseed 20 minutes; Vacuumize and stirring at low speed 30 minutes, filter, discharging (total amount 1Kg).
The preparation of B component:
Take in proportion aliphatic cyclic amine 220g, isophorone diamine 120g, aminoethyl piperazine 75g, 2,4,6-tri(dimethylaminomethyl)phenol 21g, organobentonite 6g, be placed in 2L double-planet dynamic mixing still, and middling speed stirs 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 stirs 10 minutes, adds 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 A component is stirred 3 minutes, the ratio taking in proportion in 100: 19 takes A, B component, stirrer mixes 5 minutes (or mixing with scoop), the applying glue face of being placed in, according to coat-thickness, select the notched scraper of dimension, scrape floating wholely, self-vulcanizing is more than 24 hours.
Comparative example:
Yellow color preparation: take bisphenol A epoxide resin E-51 800g, coating middle chrome pigment 200g, mix wetting with scoop; Adjust three-roll grinder rod gap, compound is crossed to roller three times, obtain yellow color.
The preparation of A component:
Take bisphenol A epoxide resin E-51 320g, epoxy resin toughener QS-BN50g, join in the planetary dispersion machine of 2L, be heated to while stirring 70 ℃ of glue temperatures, middling speed stirs 15 minutes, adds epoxide diluent 1,6 hexanediol diglycidyl ether 50g, add organobentonite 5g, dispersed with stirring 30 minutes; Add the active kaolin 37g that processes of 3000 orders; Add 1000 order white alundum powder 450g, high-speed stirring is 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 stirs 15 minutes; Add yellow color 50g (containing E-51 epoxy resin 40g), white carbon black 10g, high-speed stirring is 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 A component is stirred 3 minutes, the ratio taking in proportion in 100: 20 takes A, B component, stirrer mixes 5 minutes (or mixing with scoop), the applying glue face of being placed in, according to coat-thickness, select the notched scraper of dimension, scrape floating wholely, self-vulcanizing is more than 24 hours.
Wear-resistant, the Weather-resistant epoxy coating adhesive that above-described embodiment 1-5 is made and comparative example carry out measuring mechanical property, relative wear rate test, glass transition temperature test and the test of ultraviolet artificial accelerated aging by tackiness agent touchstone, and data are as table one, table two, table three.
1, embodiment contrasts with comparative example's measuring mechanical property, in Table 1
Table 1
Note *: be 45# steel-45# steel sandblast test piece.
Note * *: body cast exemplar ambient cure 168 hours
2, embodiment and comparative example's cut resistance test and glass transition temperature (Tg) contrast are in Table 2
Table 2
Note *: adopt cast oar type test specimen, 60%30# silicon carbide-water, 200 revs/min are continuous 72 hours.
3, embodiment and comparative example press GB/T14522-93 ultraviolet light weather resistance artificial accelerated aging test contrast, in Table 3
Table 3
Note *: adopt fluorescent ultraviolet lamp proofing box, 313nmUVB, 50-60 ℃ of condensation-illumination is respectively 4 hours periods.
Through above-described embodiment and reference examples test, testing data, contrast, embodiment has over-all properties significantly, particularly after ultraviolet artificial accelerated aging test, embodiment exemplar still has good tensile strength, and reference examples exemplar, outward appearance has presented albefaction, efflorescence, and mechanical property decay is serious.
The present invention adopts novolac epoxy resin, cycloaliphatic epoxy resin, the combination of cylohexanediol diglycidyl ether thinner, adopts the alicyclic ring amine curing agent combination that reactive behavior is higher, and the epoxy coat glue making is had: low viscosity, workability are good; Ambient cure, has higher adhesiveproperties and physical strength after solidifying; Phenolic aldehyde epoxy, cycloaliphatic epoxy resin and aliphatic cyclic amine curing system provide higher cross-linking density, make coating have good wear resistance and shock resistance; 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 aspect, have remarkable and substantial feature out of doors.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (2)
1. wear-resistant, a weathe resistance epoxy resin coating adhesive, is made with the curing agent component that is referred to as B component by the epoxy resin ingredient that is referred to as A component, and the weight ratio of A component and B component is 100: 18～22, it is characterized in that:
Described A component is comprised of the white carbon black of the alicyclic tetraglycidel ether epoxy resin of 16 parts, the novolac epoxy of 15 parts, the epoxy active diluent of 4 parts, the reactive toughening agent of 4 parts, the coupling agent of 0.5 part, the organobentonite of 0.8 part, the oxidation inhibitor of 0.3 part, the UV light absorber of 0.8 part, the white alundum powder of 40 parts, the filler powder of 5 parts, the short glass fiber of 6 parts, 5 parts of yellow colors and 1 part;
Described B component is comprised of the aliphatic cyclic amine of 25 parts, the isophorone diamine of 10 parts, the aminoethyl piperazine of 9 parts, the curing catalyst of 3 parts, the white alundum powder of 45 parts, the short glass fiber of 4 parts, the filler powder of 4 parts and the white carbon black of 5 parts;
Wherein:
Described alicyclic glycidyl ether is wherein a kind of of the saturated fat ring structure that contains two epoxy group(ing) and the oxirane value alicyclic glycidyl ether that is 0.45-0.55;
Described novolac epoxy is line style phenolic aldehyde polyglycidyl ether, and epoxy equivalent (weight) is the liquid phenolic epoxy resin that 165-175g/eq, viscosity are 9500-12000mPa.s;
Described epoxide resin reactive diluent is that oxirane value is 1 of 0.50～0.60eq/100g, 2-cylohexanediol diglycidyl ether; Described reactive toughening agent refer to there is branched structure, the CYH-277 of many active end groups;
Described coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane;
Described organobentonite is the 200 order organobentonite dry powder through surface-active-treatment;
Described oxidation inhibitor is Hinered phenols 2,6 di tert butyl 4 methyl phenol or four [methyl-β-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester;
Described UV light absorber is UV327;
During described A component forms, 5 parts of yellow colors refer to by 4 parts of cycloaliphatic epoxy resins and 1 part of prefabricated forming of coating middle chrome pigment;
Described aliphatic cyclic amine is that reactive hydrogen equivalent is the hydrogenation m-xylene diamine of 35.5g/eq;
The reactive hydrogen equivalent of described isophorone diamine is 42.6g/eq;
The reactive hydrogen equivalent of described aminoethyl piperazine is 15g/eq;
Described curing catalyst is tertiary amines promotor 2,4,6-tri-(dimethyl amine methyl) phenol;
Described filler powder refer to powder surface through coupling agent active process, finely disseminated 3000 order calcined kaolins in resin and curing component;
Described short glass fiber refers to that fine footpath is less than the short glass fiber powder of 0.5mm in 8-12um, length;
Described white carbon black refers to that specific surface area is 200m
2the fumed silica of/g.
2. the method for preparation a kind of wear-resistant, weathe resistance epoxy resin protective coating glue claimed in claim 1, is characterized in that, comprises yellow color preparation method, A method for preparing ingredients thereof and B method for preparing ingredients thereof:
Yellow color preparation method comprises:
1) take alicyclic tetraglycidel ether epoxy resin, coating middle chrome pigment, with scoop, mix wetting;
2) adjust three-roll grinder rod gap, compound is crossed to roller three times, obtain yellow color;
A method for preparing ingredients thereof comprises:
1) novolac epoxy, alicyclic tetraglycidel ether epoxy resin, reactive toughening agent are placed in to planetary dispersion machine, are heated to 70 ℃ of glue temperatures;
2) add epoxide resin reactive diluent, organobentonite dispersed with stirring 30 minutes;
3) add filler powder, white alundum powder high-speed stirring to disperse 30 minutes;
4) add short glass fiber, dispersed with stirring 10 minutes, is cooled to 40 ℃ and temperature control;
5) add coupling agent, oxidation inhibitor, uv-absorbing agent to stir 15 minutes;
6) add yellow color, white carbon black, high-speed stirring is disperseed 20 minutes;
7) vacuumize and stirring at low speed 30 minutes;
8) filtration, discharging;
B method for preparing ingredients thereof comprises:
1) aliphatic cyclic amine hydrogenation m-xylene diamine, isophorone diamine, aminoethyl piperazine, curing catalyst are placed in to 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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