CN103626912A - Aqueous acrylate emulsion adhesive for colorful metallic tiles and preparation method thereof - Google Patents
Aqueous acrylate emulsion adhesive for colorful metallic tiles and preparation method thereof Download PDFInfo
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Abstract
An aqueous acrylate emulsion adhesive for colorful metallic tiles comprises the following raw material components in percent by mass: 8-15 wt% of a hard monomer, 20-25 wt% of a soft monomer, 0.5-2 wt% of a hydroxy ester-containing monomer, 1-3 wt% of (meth)acrylic acid, 1-3 wt% of an organic fluorine-containing functional monomer, 1-5 wt% of a functional polymerizable monomer, 0.25-0.5 wt% of an initiator, 0.5-2.5 wt% of an emulsifier, 45-60 wt% of deionized water, 0.1-0.5 wt% of a buffering agent, 2-4 wt% of a pH value adjusting agent and 0.30-0.65 wt% of an auxiliary agent. Based on the structure design of a soft core and a hard casing and the synergic effect of the multiple functional monomers, not only the inherent hot sticking and cold shortness of aqueous acrylate ester emulsions is solved, but also the bonding force, the water resistance and the weatherability of the emulsion adhesive are improved; and the adhesive does not contain solvents, is strong in bonding force, good in water resistance and acid- alkali resistance and good in hot-cold alternate adaptability, and is especially applicable to the field of bonding of Al-Zn alloy coated steel sheets and colorful sand grains in the colorful metallic tiles for buildings.
Description
Technical field
The invention belongs to adhesive for building field, more particularly, the present invention relates to Al-Zn coated steel and the bonding use acrylic ester emulsion of colored sand grains tackiness agent and preparation method thereof in a kind of colored stone metal tile.
Background technology
Colored stone metal tile has natural, the simple and honest excellent decorate properties of traditional roof clay tile, has again the good use properties that modern metal tile is light and handy, firm, durable, is the senior roof cladding of current international main flow.It is applicable to the roofworks of various styles and each class formation (timber structure, steel construction, concrete structure) inclined roof building, is also applicable to the engineerings such as flat-changed-into-sloping, old roof renovation and the local decoration of buildings of existing building.It is handsome in appearance, stereoscopic sensation is strong, rich color, never fade, the feature such as environmental protection, economy, lightweight, sound insulation, fire prevention, waterproof, anticorrosive, wind resistance, shockproof, heat insulating, be the best preferred material of all kinds of high-grade roofings.
Colored stone metal tile is that to take the Al-Zn coated steel of high corrosion resistant be base material; the high-quality water-and acrylate emulsion of take is tackiness agent; the natural chad of the natural color stone particle that the height of take is weather-proof or mineral dye dyeing is aspect, the first-generation metal roof cladding of being processed into through special process.Wherein Al-Zn coated steel base material is by 55% aluminium, and the electroplate liquid that 43.4% zinc and 1.6% silicon form forms through plating, and its processibility, coating and steel plate galvanized are basic identical.Colored sand grains is ornament layer and basic unit's protective layer of metal tile, and it is that particle by certain particle diameter forms through high-tech coloring process and high temperature baking.Acrylic ester polymer as watt special adhesion material; it makes Al-Zn coated steel and colored sand grains carry out bonds well; act on very large; simultaneously as surperficial protective layer; it has played again and has prevented rain leakage, absorbs ultraviolet ray, the effects such as heat insulating; can extend the life-span of sand grains color and metal tile, guarantee the comfortable of living environment.
With tackiness agent, in use there are some defects in the colored stone metal tile that used in the market, main manifestations is, a little less than bonding force, poor water resistance, resistance to bending is bad, be subject to the easy xanthochromia of ultraviolet long-term irradiation, alternating hot and cold bad adaptability (hot sticky cold crisp), causes the quality guaranteed period of product short, and defective products is too much, caused a large amount of losses and waste, product competitiveness declines.
Therefore, study a kind of high performance colored stone metal tile use acrylic ester emulsion tackiness agent and become urgent problem.Summary of the invention
In order to solve the existing problem of prior art, the object of the present invention is to provide a kind of colored stone metal tile use acrylic ester emulsion tackiness agent and preparation method thereof, water-and acrylate emulsion binding agent adhesion property prepared by the present invention is good, water-fast and acid-proof alkaline is good, snappiness is good, thermal adaptation is strong, has the not performance of xanthochromia of long-time UV-irradiation.
Realize above-mentioned purpose, the present invention has adopted following technical scheme for this reason:
A kind of colored stone metal tile use acrylic ester emulsion tackiness agent, it is characterized in that described water-and acrylate emulsion binding agent is the raw material that comprises (methyl) acrylate monomer, functional polymerisable monomer, emulsifying agent, initiator and deionized water, the water-and acrylate emulsion that the solid content of making by emulsion polymerization is 38-45wt%.
Wherein, described (methyl) acrylate monomer comprises hard monomer, soft monomer, hydroxyl ester monomer, (methyl) vinylformic acid and containing the function monomer of organic fluorine.
Wherein, described raw material is prepared from by soft core mix monomer pre-emulsification, seed reaction, soft core mix monomer polyreaction, duricrust mix monomer polyreaction and compound process.
Wherein, described hard monomer is selected from least one in methyl methacrylate (MMA), methyl acrylate (MA), cyclohexyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, isobornyl acrylate and isobornyl methacrylate; Described soft monomer is selected from least one in butyl acrylate (BA), ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate and Isooctyl acrylate monomer (EHA); Described hydroxyl ester monomer is selected from least one in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the own ester of vinylformic acid-6-hydroxyl, methacrylic acid-2-hydroxy methacrylate and methacrylic acid-3-hydroxy propyl ester; The described function monomer containing organic fluorine is selected from least one in vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl esters, dodecafluoroheptyl methacrylate and methacrylic acid ten trifluoro monooctyl esters.
Wherein, described functional polymerisable monomer is selected from acrylamide, N hydroxymethyl acrylamide, Methacrylamide, propenal, MALEIC ANHYDRIDE, vinyl acetate between to for plastic, divinyl, vinylidene chloride, vinyl benzene, Phthalic acid, diallyl ester, trimethylolpropane allyl ether, Viscoat 295, at least one in tetramethylolmethane four (methyl) acrylate, diacrylate triglycol ester, diacetone-acryloamide(DAA) and/or AAEM.
Wherein, described emulsifying agent is selected from anionic emulsifier, nonionic emulsifying agent and reactive emulsifier composition; Wherein said anionic emulsifier is selected from sodium lauryl sulphate, Sodium dodecylbenzene sulfonate; At least one in potassium oleate, sodium oleate or succinate; Described nonionic emulsifying agent is selected from least one in Vinlub, oleic acid glyceride, ethoxylated dodecyl alcohol, lauric acid polyoxyethylene ester, polyoxyethylene oleic acid ester or tween T-60; Described reactive emulsifier is selected from 2-acrylamido-2-methyl-propyl sulfonic acid, at least one in 2-acrylamido-2-methyl-propyl sulfonic acid sodium salt, 2-vinylformic acid amido-2-methyl-propyl sulfonic acid ammonium salt, methacrylic acid hydroxide sodium dimercaptosulphanatein.
Wherein, described initiator is selected from persulfuric acid salt initiator, for example at least one in Potassium Persulphate, Sodium Persulfate and/or ammonium persulphate.
Wherein, described raw material also comprises sodium bicarbonate buffer agent and pH value conditioning agent, and described pH value conditioning agent is selected from least one in ammoniacal liquor, Monoethanolamine MEA BASF, triethylamine or 2-amino-2-methyl propyl alcohol.
Wherein, described raw material also comprises auxiliary agent, and described auxiliary agent is comprised of UV light absorber, water-based defoamer, water-based thickener and water-borne preservative.
Wherein, the quality percentage composition of described raw material is as follows: hard monomer: 8-15wt%, soft monomer: 20-25wt%, hydroxyl ester monomer: 0.5-2wt%, (methyl) vinylformic acid: 1-3wt%, containing the function monomer of organic fluorine: 1-3wt%, functional polymerisable monomer: 1-5wt%, initiator: 0.25-0.5%, emulsifying agent: 0.5-2.5wt%, deionized water: 45-60wt%, buffer reagent 0.1-0.5wt%, pH value conditioning agent: 2-4wt%, pyrodin: 0.5-1.5wt%, auxiliary agent: 0.30-0.65wt%.
A second aspect of the present invention, also provides a kind of preparation method of colored stone metal tile use acrylic ester emulsion tackiness agent.Described method is prepared from by mix monomer pre-emulsification, seed reaction, soft core mix monomer polyreaction, duricrust mix monomer polyreaction and compound process, wherein:
A, mix monomer pre-emulsification: soft monomer, part hydroxyl ester monomer, partly (methyl) vinylformic acid, part are directly added in reactor after containing the function monomer of organic fluorine and partial function polymerisable monomer raw material weighing, start stirrer, the mixed solution normal temperature emulsification 0.5 hour that adds again the deionized water of 35% emulsifying agent and 35%, makes soft core mix monomer pre-emulsion standby; Being directly added in reactor after hard monomer, remaining hydroxyl ester monomer, remaining (methyl) vinylformic acid, the remaining function monomer containing organic fluorine and remaining functional polymerisable monomer raw material weighing, start stirrer, the mixed solution normal temperature emulsification 0.5 hour that adds again the deionized water of 35% emulsifying agent and 35%, makes duricrust mix monomer pre-emulsion standby;
B, preparation seed emulsion: after emulsification, emit 75wt% emulsion, the soft core mix monomer emulsion of remaining 25wt% and whole buffer reagent, 30% emulsifying agent, 1/3 initiator and 30% deionized water are made to seeding polymerization, temperature of reaction is controlled at 85-90 ℃ of left and right, reaction times is 15-30 minute, until occur that blue light is also substantially without refluxing;
C, polyreaction: at 86-90 ℃ of soft core mix monomer emulsion that coordinate to drip residue 75wt%, whole duricrust mix monomer pre-emulsion and 2/3 initiator, the tear drop time is 120-180 minute; After dropwising, 92 ℃ of insulations 60 minutes, filter discharging after being cooled to 60 ℃, make water-and acrylate emulsion;
D, composite: after polymerization reaction kettle insulation reaction finishes, polymerization reaction kettle temperature is dropped to 50 ℃, add pH adjusting agent and water-based thickener in the emulsion in polymerization reaction kettle, the pH value of emulsion is adjusted between 8.0-9.0; Sampling and testing emulsion viscosity and solid content qualified after, in emulsion, add UV light absorber and antioxidant, water-based defoamer and water-borne preservative, continue to cool to below 40 ℃, filter discharging, obtain colored stone metal tile use acrylic ester emulsion tackiness agent finished product.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention is based on the structure design of structure of soft core duricrust and the synergy between several functions monomer and solved the intrinsic hot sticky cold crisp of water-and acrylate emulsion and the problem of resistance to bending, snappiness is good, bear dirty and be not stained with strong adaptability, economy under ash, alternating hot and cold environment, and anti-sag performance is good, good to the color developing of colored sand grains, gloss sudden strain of a muscle degree is high, and more traditional water-and acrylate emulsion binding agent is significantly increased.
(2) water-and acrylate emulsion binding agent of the present invention, by form fine and close reticulated structure in emulsion film forming process, improves bonding force, anti-impact force, the water-fast and acid-proof alkaline of emulsion binding agent.The invention belongs to low smell, nontoxic environmentfriendly products, harmless, easily degraded, not welding.
(3) bonder of the present invention has excellent weathering resistance and ageing resistance, through long-term soaked, alternating hot and cold test and damp and hot test curing membrane performance without obvious decline; In the simulation test at sunshine, adopt many group UV-lamp carry out the long-time direct projection of simulated solar and toast, without obvious Yellowing; Metal base and colored sand grains are had to good sticking power and colour developing ability, in water, one week nothing of 3 months, 50 ℃ immersions of soak at room temperature comes off, the curved test of the good T of snappiness is passed through, in the weather-proof test of alternating hot and cold sample through 20 high temperature (70 ℃)-and acid and alkali-resistance water spray (15 ℃) circulation and 20 heating (50 ℃)-freezing (20 ℃) circulate after without hollowing, the phenomenon that comes off, ftracture or be clamminess.
Embodiment
Below with reference to specific embodiment, technical scheme of the present invention is further described.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Embodiment 1
The present embodiment provides a kind of colored stone metal tile use acrylic ester emulsion tackiness agent, described tackiness agent be take (methyl) acrylate monomer, (functional polymerisable monomer, emulsifying agent, initiator, buffer reagent, pH adjusting agent, reductive agent, aqueous promoter and deionized water are raw material, the water-and acrylate emulsion that the solid content being prepared from through mix monomer pre-emulsification, seed reaction, soft core mix monomer polyreaction, duricrust mix monomer polyreaction and composite each step is 38～45%;
Its formula specifically comprises ethyl propenoate 7wt%, butyl acrylate 18, wt%, methyl methacrylate: 8wt%, methacrylic acid-2-hydroxy methacrylate: 2wt%, vinylformic acid: 2wt%, diacetone-acryloamide(DAA): 1wt%, acrylamide: 1wt%, vinylformic acid trifluoro ethyl ester: 2wt%, sodium lauryl sulphate (emulsifying agent A): 1wt%, tween T-60:0.5wt% (emulsifying agent C), 2-acrylamido-2-methyl-propyl sulfonic acid (emulsifying agent B): 1wt%, Potassium Persulphate (initiator) 0.2wt%, ammoniacal liquor (PH conditioning agent): 2.0wt%, the pyrodin of 1wt%, sodium bicarbonate: 0.5wt%, UV light absorber (TINUVIN328, vapour Bagong department product): 0.020wt%, water-based defoamer (A202, Ming Ling company product): 0.2wt%, water-borne preservative (MB-16, this company's product of hamming): 0.10wt%, water-based thickener (RHEOLATE278, this company's product of hamming): the water of 0.2wt% and surplus.
The preparation method of colored stone metal tile use acrylic ester emulsion tackiness agent on above-mentioned paper, carries out in the steps below:
A, mix monomer pre-emulsification: after the diacetone-acryloamide(DAA) of methacrylic acid-2-hydroxy methacrylate, 1.5wt% vinylformic acid, 1.5wt% vinylformic acid trifluoro ethyl ester and the 1wt% of the butyl acrylate of the ethyl propenoate of 7wt%, 18wt%, 1.5wt% is weighed, be directly added in reactor, start stirrer, add again the emulsifying agent of emulsifying agent total amount (mixture of emulsifying agent A+B+C) 35% and the deionized water mixed solution normal temperature emulsification of deionization total amount 35% 0.5 hour, make soft core mix monomer pre-emulsion standby; After the acrylamide of methacrylic acid-2-hydroxy methacrylate, 0.5wt% vinylformic acid, 0.5wt% vinylformic acid trifluoro ethyl ester and the 1wt% of the methyl methacrylate of 8wt%, 0.5wt% is weighed, be directly added in reactor, start stirrer, add again the emulsifying agent of emulsifying agent total amount 35% and the deionized water mixed solution normal temperature emulsification of deionization total amount 35% 0.5 hour, make duricrust mix monomer pre-emulsion standby;
B, preparation seed emulsion: after emulsification, emit 3/4 emulsion, remaining 1/4 soft core mix monomer emulsion and whole buffer reagent, remaining emulsifying agent, 1/3 initiator and remaining deionized water are made to seeding polymerization, temperature of reaction is controlled to 85-90 ℃ of left and right, reaction times is 15-30 minute, until occur that blue light is also substantially without refluxing;
C, polyreaction: at about 86-90 ℃, coordinate to drip residue 3/4 soft core mix monomer emulsion, whole duricrust mix monomer pre-emulsion and 2/3 initiator, about 120-180 minute of tear drop time; After dropwising, about 92 ℃ insulations 60 minutes, filter discharging after being cooled to 60 ℃, make water-and acrylate emulsion;
D, composite: after polymerization reaction kettle insulation reaction finishes, polymerization reaction kettle temperature is dropped to 50 ℃, add ammoniacal liquor, pyrodin and water-based thickener in the emulsion in polymerization reaction kettle, the pH value of emulsion is adjusted between 8.0-9.0; Sampling and testing emulsion viscosity and solid content qualified after, in emulsion, add UV light absorber, water-based defoamer and water-borne preservative, continue to cool to below 40 ℃, filter discharging, obtain colored stone metal tile use acrylic ester emulsion tackiness agent finished product.
Embodiment 2
The colored stone metal tile use acrylic ester emulsion tackiness agent that the present embodiment provides, described tackiness agent is that to take (methyl) acrylate monomer, functional polymerisable monomer, emulsifying agent, initiator, buffer reagent, pH adjusting agent, reductive agent, aqueous promoter and deionized water be raw material, the water-and acrylate emulsion that the solid content being prepared from through mix monomer pre-emulsification, seed reaction, soft core mix monomer polyreaction, duricrust mix monomer polyreaction and composite each step is 38～45%;
Its formula specifically comprises ethyl propenoate 7wt%, butyl acrylate 10wt%, Isooctyl acrylate monomer 8wt%, methyl methacrylate: 8wt%, methacrylic acid-2-hydroxy methacrylate: 2wt%, vinylformic acid: 2wt%, diacetone-acryloamide(DAA): 1wt%, N hydroxymethyl acrylamide: 1wt%, vinylformic acid trifluoro ethyl ester: 2wt%, sodium lauryl sulphate (emulsifying agent A): 1wt%, lauric acid polyoxyethylene ester: 0.5wt% (emulsifying agent C), 2-acrylamido-2-methyl-propyl sulfonic acid (emulsifying agent B): 1wt%, Potassium Persulphate (initiator): 0.2wt%, ammoniacal liquor (PH conditioning agent): 2.0wt%, the pyrodin of 1wt%, sodium bicarbonate: 0.5wt%, UV light absorber (TINUVIN328, vapour Bagong department product): 0.020wt%, water-based defoamer (A202 ，Ming Ling company product): 0.2wt%, water-borne preservative (MB-16, this company's product of hamming): 0.10wt%, water-based thickener (RHEOLATE278, this company's product of hamming): the water of 0.2wt% and surplus.
The preparation method of colored stone metal tile use acrylic ester emulsion tackiness agent on above-mentioned paper, carries out in the steps below:
A, mix monomer pre-emulsification: after the diacetone-acryloamide(DAA) of methacrylic acid-2-hydroxy methacrylate, 1.5wt% vinylformic acid, 1.5wt% vinylformic acid trifluoro ethyl ester and the 1wt% of the butyl acrylate of the ethyl propenoate of 7wt%, 10wt%, Isooctyl acrylate monomer 8wt%, 1.5wt% is weighed, be directly added in reactor, start stirrer, add again the emulsifying agent of emulsifying agent total amount (mixture of emulsifying agent A+B+C) 35% and the deionized water mixed solution normal temperature emulsification of deionization total amount 35% 0.5 hour, make soft core mix monomer pre-emulsion standby; After the N hydroxymethyl acrylamide of methacrylic acid-2-hydroxy methacrylate, 0.5wt% vinylformic acid, 0.5wt% vinylformic acid trifluoro ethyl ester and the 1wt% of the methyl methacrylate of 8wt%, 0.5wt% is weighed, be directly added in reactor, start stirrer, add again the emulsifying agent of emulsifying agent total amount 35% and the deionized water mixed solution normal temperature emulsification of deionization total amount 35% 0.5 hour, make duricrust mix monomer pre-emulsion standby;
B, preparation seed emulsion: after emulsification, emit 3/4 emulsion, remaining 1/4 soft core mix monomer emulsion and whole buffer reagent, remaining emulsifying agent, 1/3 initiator and remaining deionized water are made to seeding polymerization, temperature of reaction is controlled to 85-90 ℃ of left and right, reaction times is 15-30 minute, until occur that blue light is also substantially without refluxing;
C, polyreaction: at about 86-90 ℃, coordinate to drip residue 3/4 soft core mix monomer emulsion, whole duricrust mix monomer pre-emulsion and 2/3 initiator, about 120-180 minute of tear drop time; After dropwising, about 92 ℃ insulations 60 minutes, filter discharging after being cooled to 60 ℃, make water-and acrylate emulsion;
D, composite: after polymerization reaction kettle insulation reaction finishes, polymerization reaction kettle temperature is dropped to 50 ℃, add ammoniacal liquor, pyrodin and water-based thickener in the emulsion in polymerization reaction kettle, the pH value of emulsion is adjusted between 8.0-9.0; Sampling and testing emulsion viscosity and solid content qualified after, in emulsion, add UV light absorber, water-based defoamer and water-borne preservative, continue to cool to below 40 ℃, filter discharging, obtain colored stone metal tile use acrylic ester emulsion tackiness agent finished product.
The present invention is by comprising hard monomer, soft monomer, (methyl) vinylformic acid, hydroxyl monomer and containing the composite use of organic fluorine monomer several functions monomer and combine soft core monocoque and special seed emulsion reaction solves the consistency between each component; Make described water-and acrylate emulsion applications intrinsic hot sticky cold crisp and problem of resistance to bending when metal base bonds, snappiness is good, bear dirty and be not stained with strong adaptability, economy under ash, alternating hot and cold environment, and anti-sag performance is good, good to the color developing of colored sand grains, gloss sudden strain of a muscle degree is high, and the bonding that is applied to colored stone metal tile has excellent over-all properties.
For the ordinary skill in the art, be to be understood that and can without departing from the scope of the present disclosure, can adopt to be equal to and replace or equivalent transformation form enforcement above-described embodiment.Protection scope of the present invention is not limited to the specific embodiment of embodiment part, as long as no the embodiment that departs from invention essence, within being all interpreted as having dropped on the protection domain of requirement of the present invention.
Claims (10)
1. a colored stone metal tile use acrylic ester emulsion tackiness agent, it is characterized in that: described water-and acrylate emulsion binding agent is the raw material that comprises (methyl) acrylate monomer, functional polymerisable monomer, emulsifying agent, initiator and deionized water the water-and acrylate emulsion that the solid content of making by emulsion polymerization is 38-45wt%.
2. colored stone metal tile use acrylic ester emulsion tackiness agent according to claim 1, is characterized in that: described (methyl) acrylate monomer comprises hard monomer, soft monomer, hydroxyl ester monomer, (methyl) vinylformic acid and contains the function monomer of organic fluorine.
3. colored stone metal tile use acrylic ester emulsion tackiness agent according to claim 2, is characterized in that: described raw material is prepared from by soft core mix monomer pre-emulsification, seed reaction, soft core mix monomer polyreaction, duricrust mix monomer polyreaction and compound process.
4. colored stone metal tile use acrylic ester emulsion tackiness agent according to claim 3, is characterized in that: described hard monomer is selected from least one in methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, isobornyl acrylate and isobornyl methacrylate; Described soft monomer is selected from least one in butyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate and Isooctyl acrylate monomer; Described hydroxyl ester monomer is selected from least one in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, vinylformic acid-2-hydroxyl butyl ester, vinylformic acid-5-hydroxyl pentyl ester, the own ester of vinylformic acid-6-hydroxyl, methacrylic acid-2-hydroxy methacrylate and methacrylic acid-3-hydroxy propyl ester; The described function monomer containing organic fluorine is selected from least one in vinylformic acid trifluoro ethyl ester, vinylformic acid hexafluoro butyl ester, vinylformic acid ten trifluoro monooctyl esters, dodecafluoroheptyl methacrylate and methacrylic acid ten trifluoro monooctyl esters; Described functional polymerisable monomer is selected from acrylamide, N hydroxymethyl acrylamide, Methacrylamide, propenal, MALEIC ANHYDRIDE, vinyl acetate between to for plastic, divinyl, vinylidene chloride, vinyl benzene, Phthalic acid, diallyl ester, trimethylolpropane allyl ether, Viscoat 295, at least one in tetramethylolmethane four (methyl) acrylate, diacrylate triglycol ester, diacetone-acryloamide(DAA) and/or AAEM.
5. colored stone metal tile use acrylic ester emulsion tackiness agent according to claim 4, is characterized in that: described emulsifying agent is selected from anionic emulsifier, nonionic emulsifying agent and reactive emulsifier and forms; Wherein said anionic emulsifier is selected from sodium lauryl sulphate, Sodium dodecylbenzene sulfonate; At least one in potassium oleate, sodium oleate or succinate; Described nonionic emulsifying agent is selected from least one in Vinlub, oleic acid glyceride, ethoxylated dodecyl alcohol, lauric acid polyoxyethylene ester, polyoxyethylene oleic acid ester or tween T-60; Described reactive emulsifier is selected from 2-acrylamido-2-methyl-propyl sulfonic acid, at least one in 2-acrylamido-2-methyl-propyl sulfonic acid sodium salt, 2-vinylformic acid amido-2-methyl-propyl sulfonic acid ammonium salt, methacrylic acid hydroxide sodium dimercaptosulphanatein.
6. colored stone metal tile use acrylic ester emulsion tackiness agent according to claim 5, it is characterized in that: described raw material also comprises auxiliary agent, described auxiliary agent is comprised of UV light absorber, antioxidant, water-based defoamer, water-based thickener and water-borne preservative.
7. colored stone metal tile use acrylic ester emulsion tackiness agent according to claim 6, it is characterized in that: the quality percentage composition of described raw material is as follows: hard monomer: 8-15wt%, soft monomer: 20-25wt%, hydroxyl ester monomer: 0.5-2wt%, (methyl) vinylformic acid: 1-3wt%, function monomer containing organic fluorine: 1-3wt%, functional polymerisable monomer: 1-5wt%, initiator: 0.25-0.5%, emulsifying agent: 0.5-2.5wt%, deionized water: 45-60wt%, buffer reagent 0.1-0.5wt%, pyrodin: 0.5-1.5wt%, pH value conditioning agent: 2-4wt%, auxiliary agent: 0.30-0.65wt%.
8. colored stone metal tile use acrylic ester emulsion tackiness agent according to claim 1, it is characterized in that described tackiness agent is that to take (methyl) acrylate monomer, functional polymerisable monomer, emulsifying agent, initiator, buffer reagent, pH adjusting agent, reductive agent, aqueous promoter and deionized water be raw material, the water-and acrylate emulsion that the solid content being prepared from through mix monomer pre-emulsification, seed reaction, soft core mix monomer polyreaction, duricrust mix monomer polyreaction and composite each step is 38～45%, described water-and acrylate emulsion binding agent comprises: ethyl propenoate 7wt%, butyl acrylate 18wt%, methyl methacrylate: 8wt%, methacrylic acid-2-hydroxy methacrylate: 2wt%, vinylformic acid: 2wt%, diacetone-acryloamide(DAA): 1wt%, acrylamide: 1wt%, vinylformic acid trifluoro ethyl ester: 2wt%, sodium lauryl sulphate: 1wt%, tween T-60:0.5wt%, 2-acrylamido-2-methyl-propyl sulfonic acid: 1wt%, Potassium Persulphate 0.2wt%, ammoniacal liquor: 2.0wt%, pyrodin: 1wt%, sodium bicarbonate: 0.5wt%, UV light absorber: 0.020wt%, water-based defoamer: 0.2wt%, water-borne preservative: 0.10wt%, the water of water-based thickener: 0.2wt% and surplus, and described water-and acrylate emulsion binding agent is prepared in accordance with the following methods:
A, mix monomer pre-emulsification; After the diacetone-acryloamide(DAA) of methacrylic acid-2-hydroxy methacrylate, 1.5wt% vinylformic acid, 1.5wt% vinylformic acid trifluoro ethyl ester and the 1wt% of the butyl acrylate of the ethyl propenoate of 7wt%, 18wt%, 1.5wt% is weighed, be directly added in reactor, start stirrer, add again the emulsifying agent of emulsifying agent total amount 35% and the deionized water mixed solution normal temperature emulsification of deionization total amount 35% 0.5 hour, make soft core mix monomer pre-emulsion standby; After the acrylamide of methacrylic acid-2-hydroxy methacrylate, 0.5wt% vinylformic acid, 0.5wt% vinylformic acid trifluoro ethyl ester and the 1wt% of the methyl methacrylate of 8wt%, 0.5wt% is weighed, be directly added in reactor, start stirrer, add again the emulsifying agent of emulsifying agent total amount 35% and the deionized water mixed solution normal temperature emulsification of deionization total amount 35% 0.5 hour, make duricrust mix monomer pre-emulsion standby;
B, preparation seed emulsion: after emulsification, emit 3/4 emulsion, remaining 1/4 soft core mix monomer emulsion and whole buffer reagent, remaining emulsifying agent, 1/3 initiator and remaining deionized water are made to seeding polymerization, temperature of reaction is controlled to 85-90 ℃ of left and right, reaction times is 15-30 minute, until occur that blue light is also substantially without refluxing;
C, polyreaction: at about 86-90 ℃, coordinate to drip residue 3/4 soft core mix monomer emulsion, whole duricrust mix monomer pre-emulsion and 2/3 initiator, about 120-180 minute of tear drop time; After dropwising, about 92 ℃ insulations 60 minutes, filter discharging after being cooled to 60 ℃, make water-and acrylate emulsion;
D, composite: after polymerization reaction kettle insulation reaction finishes, polymerization reaction kettle temperature is dropped to 50 ℃, add ammoniacal liquor, pyrodin and water-based thickener in the emulsion in polymerization reaction kettle, the pH value of emulsion is adjusted between 8.0-9.0; Sampling and testing emulsion viscosity and solid content qualified after, in emulsion, add UV light absorber, water-based defoamer and water-borne preservative, continue to cool to below 40 ℃, filter discharging, obtain colored stone metal tile use acrylic ester emulsion tackiness agent.
9. the preparation method of a colored stone metal tile use acrylic ester emulsion tackiness agent, it is characterized in that described method is prepared from by mix monomer pre-emulsification, seed reaction, soft core mix monomer polyreaction, duricrust mix monomer polyreaction and compound process, wherein:
A, mix monomer pre-emulsification: soft monomer, part hydroxyl ester monomer, partly (methyl) vinylformic acid, part are directly added in reactor after containing the function monomer of organic fluorine and partial function polymerisable monomer raw material weighing, start stirrer, the mixed solution normal temperature emulsification 0.5 hour that adds again the deionized water of 35% emulsifying agent and 35%, makes soft core mix monomer pre-emulsion standby; Being directly added in reactor after hard monomer, remaining hydroxyl ester monomer, remaining (methyl) vinylformic acid, the remaining function monomer containing organic fluorine and remaining functional polymerisable monomer raw material weighing, start stirrer, the mixed solution normal temperature emulsification 0.5 hour that adds again the deionized water of 35% emulsifying agent and 35%, makes duricrust mix monomer pre-emulsion standby;
B, preparation seed emulsion: after emulsification, emit 75wt% emulsion, the soft core mix monomer emulsion of remaining 25wt% and whole buffer reagent, 30% emulsifying agent, 1/3 initiator and 30% deionized water are made to seeding polymerization, temperature of reaction is controlled at 85-90 ℃ of left and right, reaction times is 15-30 minute, until occur that blue light is also substantially without refluxing;
C, polyreaction: at 86-90 ℃ of soft core mix monomer emulsion that coordinate to drip residue 75wt%, whole duricrust mix monomer pre-emulsion and 2/3 initiator, the tear drop time is 120-180 minute; After dropwising, 92 ℃ of insulations 60 minutes, filter discharging after being cooled to 60 ℃, make water-and acrylate emulsion;
D, composite: after polymerization reaction kettle insulation reaction finishes, polymerization reaction kettle temperature is dropped to 50 ℃, add pH adjusting agent and water-based thickener in the emulsion in polymerization reaction kettle, the pH value of emulsion is adjusted between 8.0-9.0; Sampling and testing emulsion viscosity and solid content qualified after, in emulsion, add UV light absorber and antioxidant, water-based defoamer and water-borne preservative, continue to cool to below 40 ℃, filter discharging, obtain colored stone metal tile use acrylic ester emulsion tackiness agent finished product.
10. according to the preparation method of claim 9, it is characterized in that: the quality percentage composition of described raw material is as follows: hard monomer: 8-15wt%, soft monomer: 20-25wt%, hydroxyl ester monomer: 0.5-2wt%, (methyl) vinylformic acid: 1-3wt%, function monomer containing organic fluorine: 1-3wt%, functional polymerisable monomer: 1-5wt%, initiator: 0.25-0.5%, emulsifying agent: 0.5-2.5wt%, deionized water: 45-60wt%, buffer reagent: 0.1-0.5wt%, pyrodin: 0.5-1.5wt%, pH value conditioning agent: 2-4wt%, UV light absorber: 0.01-0.05wt%, water-based defoamer: 0.1-0.2wt%, water-based thickener: 0.1-0.2wt% and water-borne preservative: 0.1-0.2wt%.
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